AGC Book 20% Cyan Karl Fischer Titration

GTP Brochure

Good Titration Practice™ in Karl Fischer Titration

EDITORIAL

Dear Reader METTLER TOLEDO has an excellent knowledge in any kind of moisture and water content determination from % to ppm. It is of crucial importance to select the right analytical method in order to obtain reliable results that ensure quality and properties of the products in a multitude of industries. Karl Fischer titration is the method of choice for water content determination. With the new generation of METTLER TOLEDO compact volumetric and coulometric Karl Fischer Titrators V20/V30, C20/C30 and Excellence combined general and volumetric KF titrators T70 and T90, water determination has reached an unrivaled level of simplicity and security. This helps you to perform your daily tasks in the most optimal way. In this brochure a specific focus is put on how to perform the Karl Fischer titration analysis the correct way. We would like to introduce this to you as part of ‘Good Titration PracticeTM (GTP) in Karl Fischer titration. This brochure comprises detailed background information and recommendations about: • • • • • Chemistry and control of the Karl Fischer titration Practical tips and hints on sample preparation and instrument operation Measures to optimize accuracy and precision of the water determination Selection of the optimal method for water determination of your specific sample Trouble shooting recommendations if results do not coincide with the expectations

This GTP brochure in combination with the application brochure 39 should serve you as powerful tools for trouble-free water determination throughout the whole lifetime of your METTLER TOLEDO KF titrator. We wish you great success and enjoyment

Hans-Joachim Muhr Market Support Manager BA Titration

Rolf Rohner Marketing Manager BA Titration

.......5 Limitations for the use of the cell without diaphragm.........................................................3...................................4................3 Concentration determination with Water Standard 10........................24 4....................................................................................................1 The Control Band .........3..............7 2.................5 Application tips ......7 2.2.....2 End point and polarization current.............2 Concentration determination with di-sodium tartrate dihydrate...........................1..38 5 Sampling .........................................................1.......................2.3................13 3...........................................................4 Polarization current and end point......................................1.....................................................34 4......................2 When do you have to replace the electrolyte? ..............2 Two-component KF reagent ...4.4 Special reagents for aldehydes and ketones...............................................................................26 4..........................................2 Coulometric KF analysis...................................12 3 Titration control and end point determination....16 3...1 The influence of atmospheric humidity (drift determination) ....3.................................................................... The Karl Fischer titration.........18 3....0 mg/g .................................11 2..............................1 Volumetric KF reagents.................................2 The Karl Fischer chemical reaction .....3 Volumetric KF Titration: Titrant concentration................................1...........................................................................................................19 3................................METTLER TOLEDO Good Titration PracticeTM in KF Titration Contents 1 Fundamentals of the Karl Fischer titration ...29 4....................................33 4.........................................1 Principle of bipotentiometric indication ....9 2........2 Reaction rate ..........................................................................1.....................................................................10 2..................................6 Dissolving capacity of the solvent ....2.........2......1 Filling the coulometric cell .............................................................21 3...4...................36 4..........................3................4............................................6 Termination parameters for both coulometric and volumetric KF titration...............................6................32 4.............4 Cleaning the coulometric KF titration cell.........................................................................6 2 Volumetric and Coulometric Karl Fischer Analyses ...............1 How often should the concentration be determined?.............................26 4..............18 3.....37 4.........28 4..........................11 2.............................1..............................................................................................................3 Consequences for practical applications....................................................3 Pyridine-containing reagents .........2......4 1...................................3 The Cautious start ...........5 Control paramaters in the coulometric KF Analysis ..35 4.............5 Karl Fischer reagents with ethanol ....................3 Secure draining and filling of the titration cell: SOLVENT MANAGER...........................1 Indication ............................................................................................................................................1 One-component KF reagent ...............39 1 .......................2 Working with the coulometric KF instruments ..5 Cleaning the measuring electrode ..4 Generator electrode without diaphragm .....2 Stoichiometry of the coulometric KF rection ...............2 The minimum and maximum dosing rate .....1 KF coulometry .................................21 3..........4 Concentration determination with pure water..........33 4........1...................................................29 4.............................3 Iodine generation..........................................3 Stirring speed and dispersion of the volumetric KF titrant......26 4...........................5 The solvent.................................................................................................................................4..................13 3.....................................16 3.......................................27 4....................................22 3....................................................4 Control parameters in the volumetric KF titration .6 General recommendations ...............................................1 An historic overview ..............9 2...............................................................8 2.................4........7 2..................................................13 3............14 3.5 1.........................................2..........1 Titration stand ........1.........2...28 4.......2...................................................................................................................................8 2.......1 Using and optimizing the termination parameters for both volumetric and coulometric KF titration ...............................................20 3....................................8 2..........................19 3...............................................1....................................................................................................19 3.........................................2..2 The drift ...3.....................9 2.....................................................4 1....2.................................33 4...........

.....4 Lyophilized substance in septum bottles............................71 9....................85 11..........89 12 Appendix ..........................55 7..................................................79 11.....................2 Liquid samples ..................................54 7.........................................................5 STROMBOLI automatic oven sample changer .................5 Accessories for sample input ..........................5 Technical natural products ..................................4..........................................................................................................3 Reaction with iodine ...................................................................4...............................43 6..............1 Solids: Characteristics..........................................6 Food ...1 Resolution and detection limit ..................1........2 Purge gas.......3 External dissolution ...........................................................................................87 11..........39 5...........................................................................................................................................................................79 11........4 Manual Karl Fischer drying oven...................................58 7.......................................................1................................................2 Side reactions ........................2 Inorganic chemicals ........................................................80 11.......2 Coulometric methods .........................39 5.............................1 Organic Chemicals.............................................1 Coulometry............................81 11..............4..................................................................................75 11 Karl Fischer Titration: The Method at a Glance ......................................................1...................................................58 7...3......................79 11....................................73 10...........................................4....5 Determination of water in gases ...............................87 11....86 11..................................................72 10 Troubleshooting .............78 11................................................................77 11.....................................5 Additional literature .....73 10.....................................60 7....................................6............................................................71 9........59 7............................4 Example: reevaluation of side reactions .......................................2 Solids: Sample input ......................................................................................................................................................................1 Volumetric methods ........4.........................................................................................................................................3 Amount of sample .....43 6.3......................6............83 11..........................................2 Reaction with water..............48 7............................86 11......................78 11........................................70 9.................................................................................................................................................................57 7..................................................................................................................................2...........................................................................................................................2........................................71 9...............6...................................................................6...........................3 Repeatability .........................................67 8..................6.........1 Principle ..90 2 .......................................................................................3 Procedure............................87 11....................................................................49 7.............1...................................................70 9.......................1 Organic and inorganic chemicals ............4 Technical products .....................................................88 11........................70 9..................2 Volumetric Karl Fischer Titration .2 External extraction .40 6 Sample addition ..........................................................................................................................47 7...........................................45 7 Release of water from the sample ......................................................67 8................................................................................................1 Solid samples........................................................................................................................................................................................................1 Liquid samples .................................................................................77 11.........................................................................................................................................1 Taking the sample..........2 Storing the sample .............................4 Liquids: Sample input.................................................................80 11...............................................................................................................................................................................67 8.............................2 Measurement accuracy...............................................................1 Effects of temperature..............................3 Technical products – organic ................................................................................4 Sample preparation and input ......................3 Titration Methods ....2.................................86 11....................................58 7..........................................................................................................4....................3 Liquids: Characteristics ...........................77 11...................................inorganic ......1.......METTLER TOLEDO Good Titration PracticeTM in KF Titration 5.................................................2 Solid samples...62 8 Measurement results ....................................................................................................................1......2 Foods and technical products ........................6 References.....1 Reaction with methanol......................2............................83 11........................68 9 Interferences ..............................6 Determination using the drying oven ....1 Internal extraction ...................................

.........................92 12...............................................................96 12..............................1 One-component reagent ..........................................................6............94 12......93 12......95 12.................3 Reagents for coulometry: ...........2 For samples poorly soluble in methanol or ethanol..................METTLER TOLEDO Good Titration PracticeTM in KF Titration 12................6.....93 12..........................2 Formula for the external dissolution .........................................6 Titrants and solvents for volumetric analysis ..........5 Water Standards for Karl Fischer volumetric titration....................................95 12.............................3 Standards for Karl Fischer coulometry.4 Reagents and solvents for coulometric analysis ...4 For ketones and aldehydes..................................................................................................................4....................................4................................................96 12.......................91 12..................................91 12.5 For acids and bases (pH value) ............................................................................5 For acids and bases (pH value) ........................................1 For samples soluble in methanol or ethanol .....................95 12...................92 12.........1 For samples that are soluble in methanol or ethanol ........6.........................95 12....................6.....................4.............................................................................................................................97 13 Hazards and waste disposal tips ...........98 13............................3 For samples insoluble in methanol or ethanol......4.....98 13......................4...........98 13...............1 Formula for the external extraction ..........2 For samples that are poorely soluble in methanol or ethanol .................98 13...98 3 ......................................................6..............4 For ketones and aldehydes.90 12.......................3 For samples that are insoluble in methanol or ethanol ................................4 Safety data for the KF-components and auxiliary solvents: .........................................................................2 Two-component reagent: ..................92 12....................................

1 1935 1943 1950 1952 1955 1956 An historic overview Publication: "Neues Verfahren zur massanalytischen Bestimmung des Wassergehaltes von Flüssigkeiten und festen Körpern" by Karl Fischer [1].J. respectively. Introduction of the METTLER TOLEDO STROMBOLI KF Oven Sample Changer. promoted by publications by E. “Testing of mineral oil hydrocarbons and solvents: Determination of water content according to Karl Fischer . and solvent dispensing and removal. DO185 Drying Oven for the DL18 Karl Fischer Volumetric Titrator. 2000 2001 2002 2008 4 .Boyd [4]. Introduction of less poisonous KF reagents based on ethanolic solution. Peters and J.Direct method”). Publication: “The Dead-Stop End Point“. Jungnickel. D. First microprocessor controlled KF titrator (METTLER DL18) with automatic drift compensation. Pyridine-free KF reagents are commercially available. Use of Karl Fischer method spreads. First coulometric KF titration instruments are commercially available. First fully automatic KF titration with laboratory robots (METTLER DL18 and ZYMARK). Enormous spread of the use of KF titration. by G. S. DL37 KF Coulometer from METTLER TOLEDO. Wernimont and F. M. Eberius [3]. They replaced the DL18/35 KF Volumetric Titrators. 1959 1960 1970 1980 1984 1985 1989 1990 1995 1997 1998 New DV705 KF Titration Stand with very low drift value (< 2μg/min) for the METTLER TOLEDO DL53/55/58. Pyridine-containing two-component reagents and dead-stop titration instruments are commercially available. Meyer and C. Publication: Coulometric Karl Fischer Titration by A. First diaphragm-less cell for coulometric KF titration.3 First titrator (METTLER TOLEDO DL55) with online curves E = f(t) and V = f(t) for Karl Fischer titration.METTLER TOLEDO Good Titration PracticeTM in KF Titration 1 Fundamentals of the Karl Fischer titration 1. Solid KF Oven Standards with water contents of 5. Hopkinson [2].1 mg/g) with test certificate according to DIN 50049-2.0. April 1956. Automatic KF titration instruments with piston motorized burettes. titrant specific standard parameters and LEARN titration. L. Improved METTLER TOLEDO DO307 KF Manual Drying Oven. Publication on stabilized single-component Karl Fischer reagent by E. METTLER TOLEDO RONDO Sample Changer with Karl Fischer Kit for automated KF volumetric determination. First German DIN standard for the Karl Fischer titration (DIN 51777. Water standards (10. 0.5% and 1%. 1. Introduction of the METTLER TOLEDO DL32/39 KF Coulometers (generating cell with and without diaphragm). Introduction of the METTLER TOLEDO Titration Compact Line V20/V30 and C20/C30 Karl Fischer Instruments.0. and DL67/70ES/77 Titrators Introduction of the METTLER TOLEDO DL31/DL38 KF Titrators with dedicated fuzzy logic control.

Karl Fischer used pyridine for this purpose. all the sulfur dioxide is present as methyl sulfite. the more methyl sulfite is formed by the capture of protons. the 5 . In the pH range 5. This is formed from sulfur dioxide and methanol according to the equation: 2 CH3OH + SO2 → CH3OH2+ + CH3OSO2- The higher the pH of the solution. Bunsen [5]: Karl Fischer discovered that this reaction could be used for water determinations in a nonaqueous system containing an excess of sulfur dioxide [1]. Py•SO3 + H2O → 2 Py-H+I– + Py•SO3 – Py-H+HSO4 – Further studies conducted by J. and the faster the rate of the Karl Fischer reaction. Bryanz and Mitchell [6] formulated a two-step reaction: 1. it is necessary to neutralize the acids that are formed during the process (HI and H2SO4). In order to achieve an equilibrium shift to the right. I2 + SO2 + 3 Py + H2O → 2. depends on the pH value of the medium (see graphics below) -d[I2]/dt = k • [I2] • [SO2] • [H2O] One possible explanation for the influence of pH on the reaction rate is that it is not the sulfur dioxide itself that is oxidized by iodine under the influence of water. i. the reaction between iodine and water takes place in the stoichiometric ratio of 1:2: 1. The rate of the Karl Fischer reaction. In an alcoholic solution. Methanol proved to be suitable as a solvent. Py•SO3 + CH3OH → 2 Py-H+I– + Py•SO3 – Py-H+CH3SO4 According to these equations. C. Smith. Verhoff and E.2 The Karl Fischer chemical reaction I2 + SO2 + 2 H2O → 2 HI + H2SO4 The water content determination is based on the reaction described by R. the reaction between iodine and water takes place in the stoichiometric ratio of 1:1. Barenrecht [7] on the subject of the Karl Fischer reaction have revealed that: • • Pyridine is not directly involved in the reaction. W. At pH values above 8. methanol not only acts as a solvent but also participates directly in the reaction itself. described by the rate constant k.METTLER TOLEDO Good Titration PracticeTM in KF Titration 1. I2 + SO2 + 3 Py + H2O → 2. but rather the methyl sulfite ion.e.5. the maximum reaction rate is reached here and cannot increase further..5 to 8. In an alcohol-free solution. it only acts as a buffering agent and can therefore be replaced by other bases.

Methanol should therefore always be present in the minimum required amount. Experiments on the stoichiometry of the reaction showed that methanol can in fact be replaced by other alcohols (e. This improves the titer stability.g. this results in a more sluggish endpoint and higher iodine consumption. methanol) (e. in a titration. you can use other alkohols such as.3 • Consequences for practical applications Influence of pH on the Karl Fischer reaction Since the maximum rate of the Karl Fischer titration is in the pH range 5. In 1988. ROH + SO2 + RN 2. This reagent not only replaced the toxic. pungent pyridine. Verhoff and E. Scholz was also able to confirm the existence of basic methylsulfite in methanol/SO2/I2 solutions during the titration. A. for instance. This. is not a serious limitation because the water concentration in the solvent is usually much less. and references therein]. → → (RNH) · SO3 R (RNH) · SO4 R + 2 (RNH)I 1. (RNH) · SO3 R + 2 RN + I2 + H2O This resulted in the general chemical equation: ROH + SO2 + 3 RN + I2 + H2O → (RNH)•SO4 R + 2 (RNH)I E.METTLER TOLEDO Good Titration PracticeTM in KF Titration reaction rate increases due to side reactions between iodine and hydroxide or methylate ions. for determination in ketones or aldehydes). pH values less than 4 and greater than 8 should be avoided in practice. 6 .g.g. Scholz developed a pyridine-free Karl Fischer reagent with imidazole as base [8].C. dimethylformamide) Studies by Eberius [3] showed that iodine and water react in the ratio of 1:1 if the percentage of methanol in the solvent is 20% or more. ethanol. Scholz resulted in the following reaction scheme being proposed for the Karl Fischer reaction [8]: 1. however. Barendrecht [7] observed an increase in the titer with water contents greater than 1 mol/L. 2-propanol. you should adjust the pH value to the ideal range by adding buffering agents (for acids: imidazole. ethylene glycol monomethyl ether. E. J.g. Seubert [9] identified methylsulfite in KF solutions with the aid of IR spectroscopy and isolated and identified methyl sulfate as the secondary product of the KF reaction. On the basis of this knowledge. • Influence of the water content of the sample on the Karl Fischer reaction The water content of the sample also influences the H2O:I2 molar ratio.5 to 8. Studies by E. but also facilitated faster and more accurate titrations because imidazole buffers in a more favorable pH range than pyridine. diethylene glycol monoethylether) [10. If a methanol-free titrant has to be used (e. and for bases: salicylic acid). With acidic or basic samples. • Influence of the solvent on the Karl Fischer reaction The stoichiometry (molar ratio of H2O:I2) depends on the type of solvent: Alcoholic solvent Non-alcoholic solvent H2O:I2 = 1:1 H2O:I2 = 2:1 (e. methoxyethanol.

where a solution containing iodine is added using a motorized piston burette.e.METTLER TOLEDO Good Titration PracticeTM in KF Titration 2 Volumetric and Coulometric Karl Fischer Analyses The determination of the water content according to Karl Fischer is nowadays performed by two different techniques: – – Volumetric Karl Fischer Titration. is approximately 0. the decrease in concentration. i. Coulometric Karl Fischer Analysis.100% Coulometric Karl Fischer Analysis Iodine is generated electrochemically during titration. dissolved in a suitable alcohol. The solvent is methanol..5 mg/mL per year in a sealed bottle. The reagent can be stored for approximately two years.5% 2. The reagent is available in three different concentrations: 5 mg/mL for samples with a water content of 1000 ppm to 100%. You can also use a methanolic solvent mixture specially adapted to the sample as the solvent. where iodine is generated by electrochemical oxidation in the cell The selection of the appropriate technique is based on the estimated water content in the sample: Volumetric Karl Fischer Titration Iodine is added by a burette during titration. The drop in titer. 1 mg/mL for samples with a water content of less than 200 ppm. Suitable for samples where water is present as a major component: 100 ppm . sulfur dioxide and imidazole. Suitable for samples where water is present in trace amounts: 1 ppm .1 Volumetric KF reagents 2.1 One-component KF reagent The titrant contains iodine. 2 mg/mL for samples with a water content of less than 1000 ppm.1. 7 .

which allow for fast and accurate Karl Fischer titrations. As a result. High titration speed. sulfur dioxide and 2-methoxyethanol. leading to higher water contents and a vanishing end point.g. reagents containing pyridine are still used because they are cheaper and can be made in-house. such as amines. favorably priced. Some manufacturers have slightly increased the pyridine content in the titrant to achieve a higher titration speed.g. additional water is produced and titrated at the same time.4 Special reagents for aldehydes and ketones Aldehydes (R-CHO) and ketones (R-CO-R) form acetals and ketals if titrated with standard methanol-containing reagents. e. increases their lifetime. imidazole and methanol.1. from Sigma-Aldrich) and e. Reagents One-component Two-component 2. To improve stability. titration speed slower. dissolved in methanol. 2 mg/mL for samples with a water content of less than 1000 ppm. – Titer less stable. One-component reagent: The titrant contains iodine. Solvent capacity restricted. 8 . A titration speed two or three times as high can be achieved with the two-component reagent. Two-component reagent: The titrant contains iodine dissolved in an alcohol.1. e. + Simple handling. The titrant has a stable titer. It is available in two different concentrations: • • 5 mg/mL for samples with a water content of 1000 ppm to 100%. The separation into titrant and solvent improves stability of the KF reagents. stable titer. from VWR/MERCK) are commercially available to prevent this problem.g. imidazole. pyridine. provided that the bottle is tightly sealed. apura® (CombiTitrant 5 Keto with CombiSolvent Keto. whereas the solvent contains 2-chloroethanol and trichloromethane. These solutions are mixed 1:1 just before use to form the one-component titrant. The solvent contains sulfur dioxide.2 Two-component KF reagent The titrant contains iodine and methanol. methanol). The solvent is either methanol or consists of methanol mixtures. sulfur dioxide and pyridine.3 Pyridine-containing reagents Despite the existence of pyridine-free reagents. methanol. Both the components are very stable in storage. imidazole.1. methanol) and B (iodine. or an alcoholic mixture. Note that it may be necessary to adapt the end point value in the titration method to these reagents. dissolved in an alcohol (usually methanol). 2. whereas the solvent consists of sulfur dioxide and a base. some manufacturers also sell the titrant separated into solution A (sulfur dioxide. One-component reagent: The titrant contains iodine. HYDRANAL® (Composite 5K and Working Medium K. This special reagent is also suitable for substances that react with methanol. This reagent is declared as “rapid”. The titration takes slightly longer than with the standard KF reagent.g. Special methanol-free KF one-component reagents such as e.METTLER TOLEDO Good Titration PracticeTM in KF Titration 2. and results in higher titration speed.

diethanolamine and ethanol. * The terms "generator electrode" and "measuring electrode" mean an arrangement of two electrodes (anode and cathode) to form an electrolytic cell. These reagents also allow for titration of several ketones which form ketals considerably more slowly in ethanol than in methanol. ROH + SO2 + 3 RN + I2 + H2O → (RNH)•SO4 R + 2 (RNH)I In coulometry. the iodine is generated electrochemically by anodic oxidation in the coulometric cell according to the following half-reaction: 2 I .5 Karl Fischer reagents with ethanol Since ethanol is less toxic than methanol. which is monitoring the potential of the sample solution by voltametric technique during coulometric titration. 9 . imidazole.1 KF coulometry Coulometric KF determination of water is based on the standard reaction equation for the KF reaction. 2. The generator is close to the measuring electrode*. a double pin platinum electrode. The classical coulometric cell consists of two parts. or “inner burette”) incorporated into the glass titration cell. ethanol-based reagents were launched in 1998.METTLER TOLEDO Good Titration PracticeTM in KF Titration 2. whereas the solvent contains sulfur dioxide.2 Coulometric KF analysis 2. The titrant contains iodine and ethanol.→ I2 + 2 e Iodine generation occurs at a generator electrode* (also called “generator cell”. two-component. the anode compartment and the cathode compartment. Both parts are separated by a diaphragm.2.1. however.

CH3SO3H. is the quantity of charge that is transported by a current of 1 ampere in one second. Depending on the application. other solvents such e. it is known that to produce one mole of a chemical substance that requires one electron. C. Anode reaction At the anode. can reach the cathode where it is reduced to a sulfide compound (obnoxious smell!). iodine is generated from iodide by electrochemical oxidation.e. C. The negative iodide ions release electrons at the anode and form iodine. An ammonium salt is added to the catholyte in order to promote hydrogen production.→ I2 → H2O 10 . 2 [RN]H+ + 2e. 2 I. it is necessary to first recall the definition of 1 Coulomb: one coulomb. This can cause the cathode to become black. iodine reacts with water. 96485 C of current are needed. Methanol or ethanol is used as solvent. The cathode compartment contains the catholyte. To avoid this.→ H2 + 2 RN Ammonium ions are then reduced with the formation of hydrogen and a free amine.e. In Karl Fischer reaction two iodide ions. as chloroform. 2. This is the main product formed. Cathode reaction At the cathode. the KF electrolyte which is required for the oxidation in order to generate iodine by applying a current at the generating electrode. are oxidized to one molecule of iodine. To calculate it. I-.2 Stoichiometry of the coulometric KF rection The amount of water titrated by coulometric technique is determined by the amount of electrical current given in Coulomb. i.g. The catholyte is either a manufacturer-specific special reagent. 1C=1A·1s On the other hand. the reagent that enables completion of the whole electrochemical reaction: the oxidation reaction in the anolyte compartment is completed by a reduction reaction in the catholyte compartment. which subsequently reacts with water. used to generate iodine. Note that methyl sulfonic acid. present in the anolyte compartment.METTLER TOLEDO Good Titration PracticeTM in KF Titration The anode compartment contains the anolyte. i. the catholyte should be replaced once in two weeks. or the same reagent as used in the anode compartment. This consists of sulfur dioxide. imidazole and iodide salts. releasing two electrons at the anode. octanol. Subsequently. I2. hexanol or ethylene glycol may be added. the positive hydrogen ions are reduced to hydrogen. The value 96845 C/mol is known as the Faraday constant.2.

the conductivity of the anolyte is influenced by the samples and additional solvents (chloroform.2. For this reason.712 C electrical current. The main advantages compared to cells with diaphragms are: no contamination or blockage of the diaphragm easier cleaning lower drift 11 . it is strongly recommended that the coulometer is regularly checked by measuring a certified water standard. Nevertheless. this calculation can be expressed as follows: 1 mg of water corresponds to a consumption of 10.). Since current and time can be accurately measured. etc. Since the molar mass of water is 18.4 Generator electrode without diaphragm with diaphragm without diaphragm The first commercially available diaphragmless cell for KF coulometry was introduced in 1989. The maximum pulse height depends on the following factors: conductivity of the anolyte voltage at the generator electrode surface of the generator electrode The voltage at the generator electrode and the surface of the electrode depend on the type of coulometer.METTLER TOLEDO Good Titration PracticeTM in KF Titration Therefore.015 g/mol. In addition. hexanol. For an electrochemically optimized Karl Fischer cell.3 Iodine generation Iodine is generated by means of current pulses of 400. the coulometer operates with current pulses of 400 mA. coulometry is designated as absolute method. 200 and 100 mA. 2. it is used as a reference method for the determination of water content. the current conversion efficiency for iodine production is assumed to be 100%. 300. less than 3–4 μS/cm).2. At very low conductivities (i. This gives an iodine generation rate which corresponds to a maximum of 2240 μg water/min. 2. As a consequence. The rate of iodine generation is adjusted by varying the pulse duration and frequency and the pulse height (in mA). the maximum possible current applied by the instrument is 100 mA. 2 x 96485 C/mol is required for 1 mole of water. With standard conductivity values. no standardization of the coulometric KF reagents is necessary.e.

12 .METTLER TOLEDO Good Titration PracticeTM in KF Titration Originally. In practice. Thus. and for very accurate determinations. this makes it almost impossible for iodine to reach the cathode and be reduced to iodide. especially when easily reducible. especially for nitro compounds such as nitrobenzene. This effect is further enhanced by the small dimensions of the cathode.chlorinated hydrocarbons alcohols . The latter can thus react more efficiently with water.edible oils petroleum oils A cell with diaphragm is required for: samples with a very low water content (< 50 μg water/sample) very accurate determinations nitro compounds unsaturated hydrocarbons.ethers ketones (with special reagent) .acetamides etheric oils and essences .2. other easily reducible substances such as unsaturated fatty acids. Nascent hydrogen is formed at the cathode.g. the cell with diaphragm may yield more precise results.phenols (most) esters .e. the cathode is a small-size pin). etc. may also be reduced at the cathode by the formation of water. the relative error due to this effect can be minimized by using a larger amount of sample. The purpose is to prevent that iodine molecules generated at the anode are immediately reduced to iodide ions at the cathode instead of reacting with water. Note that hydrogen gas generated at the cathode is forming gas bubbles around its surface. This is a very good reducing agent. In addition. a relatively high stirrer speed allows for more rapid distribution of the generated iodine molecules. the generator cell was first built with a porous ceramic frit (diaphragm) separating the inner cathode compartment from the anode compartment. lower than 50 μg water/sample).5 Limitations for the use of the cell without diaphragm The cell without diaphragm is not suitable for samples that are easily reduced. R-NO2 + 3 H2 → R-NH2 + 2 H2O Besides this. The diaphragmless cell is ideal for the determination of the water content of the following compounds: hydrocarbons . a different geometry is used for the generating cell without diaphragm. for measurement of samples having a very low water content (e.. To avoid this concurring reaction. However. The cathode is smaller and made in such a way that iodine cannot reach the cathode (i. 2. it is still possible for a very small amount of iodine to reach the cathode. Nevertheless.

the stirring speed and mixing of the sample solution. . the water content.the reaction rate of the Karl Fischer reaction . Ideally. there is no free iodine in the titration/anolyte solution.the termination of the analysis. 3. • • As long as the added iodine reacts with the water. . When the voltage drops below a defined value.1 Principle of bipotentiometric indication A bipotentiometric indication is used for the volumetric Karl Fischer titration as well as for the coulometric analysis (in electrochemical terminology this is also called "2-electrode potentiometry"). iodine should be added or generated as quickly as possible. .1 Indication 3. and hence. Free iodine causes ionic conduction and the voltage needs to be reduced to keep the polarization current constant.the control algorithm and its parameters. 13 . The resulting titration speed depends on the following factors: . The control of the titration is only possible if the end point is indicated. • • • As soon as all the water has reacted with iodine. and the addition or production stopped exactly at the end point. A high voltage is necessary to maintain the specified polarization current at the electrode. Only then can the titrant consumption or the generated iodine amount be determined with the desired accuracy. the titration is terminated. A small. there will be free iodine in the titration solution.METTLER TOLEDO Good Titration PracticeTM in KF Titration 3 Titration control and end point determination The addition or generation of iodine must be controlled.1. constant AC current – the polarization current "Ipol" – is applied to a double pin platinum electrode.the viscosity of the solution and its temperature.the addition speed or generation rate of iodine .

this value depends on the polarization current. respectively. The iodine is present only at low concentration. . the titration end point is reached if the potential at the polarized platinum double pin electrode drops below a specific predefined value. Ionic conduction Iodine takes up an electron at the negatively charged platinum pin of the indicator electrode and is thereby reduced to iodide (I-). It then acquires two electrons and turns into iodide ions (2 I–).METTLER TOLEDO Good Titration PracticeTM in KF Titration • The ionic conduction takes the following course: an iodine molecule is attracted by the negatively charged platinum pin. This drop in voltage is used to indicate the end of the titration.(to a lesser extent) the type of electrode (i. The end point value mainly depends on . Now a low voltage of 50 mV to 100 mV is required to keep the polarization current constant.1. Above all.e. i. • • At the beginning and during the titration: As long as the iodine generated reacts with the water. Iodide ions. Thorough mixing of the titration/anolyte solution is necessary in order to achieve constant "ionic conduction". A voltage of ca. This free iodine gives rise to "ionic conduction". 400 mV to 650 mV is necessary to maintain the set polarization current at the double pin electrode. there is no free iodine in the titration/anolyte solution. 3. The two negatively charged iodide ions are attracted by the positively charged platinum pin. Ipol . no iodine reaches the negatively charged platinum pin.the polarization current. 14 . geometry and dimensions of the metal parts) . again.the solvent or anolyte used in the instrument. where they donate the electrons and form an iodine molecule. This leads to a termination of "ionic conduction" and the measurement signal becomes unstable.2 End point and polarization current The Karl Fischer titration is terminated when an excess of iodine is detected in the titration cell. I2. which are present in excess in the titration solution. then releases the electron again at the positively charged platinum pin and is again oxidized to iodine. free iodine is present in the titration/anolyte solution. If mixing is poor. At the end of the titration: As soon as all the water in the sample has reacted with the iodine.e.

pin diameter: 1 mm): AC Polarization current / µA 5 Endpoint / mV 100 The same end point values can be used for ethanol based KF coulometric reagents. just after the equivalence point. a double ring or plates instead of rings. and subsequently it remains constant. a layer is formed on the surface of the platinum pin sensor. 15 . The condition of the sensor has an influence on the potential jump Platinum is a strongly adsorbing metal. on the other hand. Which polarization current should be used? A higher polarization current requires a larger iodine excess (indicated by a pronounced yellow coloration of the titration cell solution) to achieve ionic conduction for the determination of the end point. and increases the risk of over titration. However. The layer is formed during the first ten titrations. In general the larger the platinum surface the smaller the current density. Sensors with a large platinum surface. i. pin length: 3 . As a consequence. the polarization current should be set as low as possible. its surface can easily bond suitable chemical compounds. On the other hand. exhibit a smaller potential jump. pin length: 3 to 4 mm. e.g.e. With use. a lower polarization current gives a smaller and steeper potential jump at the end of the titration. the following values have been obtained with a C20/C30 KF Coulometer (double pin platinum sensor. The current density can be compared to a water pipe where a specific water has to flow. i. The larger the diameter of the pipe.e.4 mm. Influence of the sensor The potential jump at the end of the titration is also influenced by the geometry (surface and design) of the platinum sensing material of the sensor. the following end points have been defined for methanolic one-component and two-component KF reagents using a V20/V30 volumetric KF titrator or T70/T90 Excellence titrator (double pin platinum electrode. the lower the pressure needed to transport the desired amount of water through the pipe (= smaller pressure difference). with longer pins. pin diameter: 1 mm): AC Polarization current / µA 24 Endpoint / mV 100 For the coulometric KF analysis.METTLER TOLEDO Good Titration PracticeTM in KF Titration For the volumetric KF titration. exhibit a larger potential jump and also a higher end point. This makes it more difficult to stop the titration at the right moment. iodine excess should be as low as possible to get accurate results. Sensors with short platinum pins (< 3 mm). With used sensors. and increases the sensor resistance. this leads to a larger potential jump compared to a cleaned or a new sensor (without layer).

the water concentration. Iodine generation or addition can proceed rapidly because iodine immediately reacts with water. [I2] .2 min with a titrant consumption of 2. and the reaction rate also decreases: iodine must be generated or added more slowly because a small water amount is still present. If the speed is too slow. At the beginning.the sulfur dioxide concentration. which gives a high reaction rate. This results in a reaction rate up to 2 times faster for the two component reagent than for the one component reagent. sulfur dioxide is present in large excess in the anolyte. shape of the vessel (volumetric KF titration).0 mL In the coulometric KF analysis. point of titrant addition (volumetric KF titration). with the twocomponent reagents. irregular. the pH value of the solution has a strong influence on the rate and in particular on the stoichiometry of the Karl Fischer reaction.d[I2] / dt = k · [I2] · [SO2] · [H2O] In addition.METTLER TOLEDO Good Titration PracticeTM in KF Titration 3. [SO2] . the water concentration is lower. Iodine generation or addition is usually the rate determining factor. 3. note that sulfur dioxide is added only in slight excess with the iodine titrant solution when using one component titrant. It is consumed with each additional measured sample leading to a decreasing dioxide concentration. Karl Fischer titrations with the two component reagent are thus significantly faster than with the one component reagent. In the volumetric KF titration. If 16 .and on the iodine concentration. Towards the end of the titration.5 . Stirring speed The optimum stirring speed is obtained when a distinct vortex is visible. [H2O] . and overtitration may occur. 3.3 Stirring speed and dispersion of the volumetric KF titrant Good mixing is essential for fast and accurate KF titrations. On the other hand. a large excess of sulfur dioxide is present in the solvent. As a consequence. 2.0 mL 1. Mixing is influenced by the 1. lower reaction rates are achieved with anolyte solutions that have been used for a long time. Example (V20/V30/T70/T90): One-component reagent Two-component reagent 2-3 min with a titrant consumption of 2. stirring speed.2 Reaction rate The reaction rate of the Karl Fischer titration depends on: . the water content is high. the titration may also be too slow.

the stirring speed is too fast. Vessel shape The conical shape of the beaker and the short stirring bar lead to turbulence at the point of titrant addition that effectively disperses the titrant. Bubbles falsify the measured values. Iodine would not be distributed upwards. Furthermore. 17 . leading to slower addition and longer titration time. but rather along the base directly towards the sensor. Point of titrant addition The titrant should be added where the turbulence is the greatest to ensure efficient mixing.METTLER TOLEDO Good Titration PracticeTM in KF Titration bubbles form into the solution. turbulence is not achieved and the mixing effectiveness is lower. the point of addition should be sufficiently far away from the sensor to allow for sufficient time for reaction. Otherwise the sensor may directly detect added iodine. This is essential for a fast reaction rate and for short titration times. If a longer stirring bar is used.

The following drawing reveals a schematical illustration of the control band: 18 .1 The Control Band The control band is a modifiable control parameter for both types of KF reagents. The dynamic behaviour of the control can be influenced by a variation of the control band.4 Control parameters in the volumetric KF titration Several parameters can be defined in the titration method in order to optimize the method for the samples and the reagents.4. An overview of the control parameters is given as follows: Volumetric KF Titration End point Control band Dosing rate (max) Dosing rate (min) Start: Normal.METTLER TOLEDO Good Titration PracticeTM in KF Titration 3. The recommended standard values are listed in the following table: Recommended standard values Sensor Ipol [µA] Stirrer speed [%] End point [mV] Control band [mV] Dosing rate (min) [µL/min] Dosing rate (max) [mL/min] Start Driftstop relative [µg/min] 1-Comp titrant 24 35 100 400 80 5 normal 15 2-Comp titrant 24 35 100 400 100 3 normal 15 3. Cautious The volumetric KF methods of the V20/V30 as well as T70 and T90 use KF titrant specific titration control parameters.

the titration starts so quickly that overtitration may occur. 3.g.e. if the polarization current changes. 2. the control reacts more sensitively to potential changes.The dynamics of the control can be influenced in the following way: Increase of the control band Aggressive control Smooth control Two different controls are used for 1-Comp and 2-Comp titrants. i. This is more suited for small water amounts. if the control band width is decreased.4 Polarization current and end point Each end point is valid for a specific polarization current. at higher water contents. You should select Start: Cautious for one and two component reagents if the amount of water in the sample is less than 500 µg. Thus. 3.3 The Cautious start If the water content is very low.4.4. Recommendations 1. The following points represent possible contributing factors: contaminated or old sensors. the slower is the titrant addition. The end point for a specific polarization current is influenced by the sensor and the solvent. the titrator automatically issues a warning. 3. The closer the potential to the end point. In both cases (normal and cautious mode) the maximum dosing rate will be reached at the end of the ramping up. The maximum dosing rate is dependent on the actual burette size. the titration will take too long. Dosing rate (max) = 2 mL/min. 19 .METTLER TOLEDO Good Titration PracticeTM in KF Titration The titrant addition is calculated on one hand by using the distance of the actual potential from the end point and on the other by using dE/dt.. In particular. You can also set the maximum dosing rate to a lower value for small amounts of water if you wish the titration to progress more cautiously. The 2-Comp titrant control reacts more sensitively to a potential drop than the 1-Comp titrant control.2 The minimum and maximum dosing rate Both rates limit the dosing speed of the titrant to an upper or lower level. Burette size [mL] 1 5 10 20 Maximum dosing rate [mL/min] 3 15 30 60 Remark: Since the maximum dosing rate of a 1 mL burette is lower than the standard parameter 5 mL/min in the case of a 1-Comp titrant. With large amounts of water. which leads to a stronger reduction of the dosing speed. the titration starts with a slower acceleration (ramp up) than in the normal mode.4. In the cautious mode. however. the end point must be adjusted. longer titration times and poorer repeatability are resulting by selecting a higher end point potential value. e. sensors with very short platinum pins (< 3 mm). In this case you can activate the Start: Cautious parameter.

the overall ionic conductivity is decreased. Therefore the potential jump at the end of the titration is smaller compared to conventional reagents. instead of methanol or ethanol. this results in an illdefined titration end point. the sensor current shall be reduced to 15 μA. the maximum dosing rate can be set higher for certain reagents: 4 mL/min for Riedel de Haen 2-Comp 5. Therefore it is recommended to decrease the polarization current to about 15 μA.g.5 Application tips Methanol based reagents • The standard parameters listed in the table above are ideal for the titration with methanol-based reagents.METTLER TOLEDO Good Titration PracticeTM in KF Titration - long alkyl chain alcohols. e.g. Auxiliary reagents • If formamide is added to the solvent. • If 1-comp titrants are used. the control band shall be decreased to 100 mV and the maximum dosing rate decreased to about 50%. The consequences of choosing a too low end point value are illustrated in the figures above: On the right side. 20 .4. the overall ionic conductivity is increased. If 2-comp ethanolic reagents are used. the titration curve is more or less flat towards the end. up to 8 mL/min for most 2-Comp 2 titrants. the system reacts slowly in the case of ethanol based reagents. which will lead to long titration times and to low precision. • • If 1-Comp titrants are used with Ethanol (e. the titration can be accelarated by reduction of the control band to 300 mV. This results in a lower voltage required to maintain the polarization current. • If 2-comp titrants are used. used as solvent. 2-propanol. Composolver E) the standard 1-Comp parameters (cf. • If Chloroform or Xylene is added in order to dissolve oil samples. table) work fine. In order to achieve a good repeatability. 3. If one-component reagents are used. setting up of the titrant as 1-comp KF titrant yields shorter titration times. Ethanol-based reagents • Compared to the methanol-based reagents. This measure allows the system to cope with the reduced conductivity.

However the control band shall not exceed the start potential. 200. where the methanol has been replaced by e. Cautious Generator current: Automatic. 100 mA) 21 . Furthermore it is recommended to reduce the polarization current to a value of 15 μA. E E t Oscillating system behaviour. There is no need to accurately adjust the control band to the actual start potential. The most straight forward influence on the control behaviour is achieved by a variation of the maximum dosing rate. which is the case in 1-Comp systems. 3. In general.METTLER TOLEDO Good Titration PracticeTM in KF Titration KF reagents for ketones • An end point value of 150 mV for both one-component and two-component reagents is recommended when using special KF reagents for aldehydes and ketones.6 General recommendations 1. In most cases 300 – 400 mV are well-suited.4. 2-methoxyethanol. This control is also recommended for 2Comp systems that show a noisy signal at the beginning of the titration. 3. which is the case in some ethanolic reagents. If the titration takes too long. the 1-Comp control is suitable for systems that show an oscillating potential behaviour. The minimum dosing rate shall be used to fine tune the final phase of the titration. an increase of the control band is recommended. In the case of 2-comp reagents over titration can be prevented by reduction of the maximum dosing rate. ->Use the 1-Comp control Smooth system behaviour ->Use the 2-Comp control t 3. 2. 300.g.5 Control paramaters in the coulometric KF Analysis An overview of the relevant control parameters is given as follows: End point Control band Rate: Normal. Fix (400.

i. Normal: This iodine generation mode is generally used for all water content determinations. Initially. More specifically. absolute drift stop. Cautious: Suitable for samples of low water content (e. Five termination parameters can be defined in the titration method: delay time. high resolution burettes (0. The fixed setting is used for solutions that exhibit a difficult characteristic with respect to conductivity. 3. less than 50-100 μg water per sample). 2. i. Since the first developed KF reagents reacted slowly. maximum titration time.g. the slope of the iodine generation rate is flat at the beginning of the titration. the iodine generation is higher than in the cautious mode. During the course of the titration it increases up to the maximum rate at a generating current of 400 mA. it has been possible to reduce the delay time to 5 to 10 seconds due to the introduction of • • • new. tightly sealed stand). During the course of the titration it increases up to the maximum rate at a generating current of 400 mA. iodine is generated by means of current pulses of 400. In particular. 300. as soon as the was potential value was lower than the set end point during the defined delay time. In addition.. relative drift stop. the slope of the iodine generation is steeper and the rate is increased based on the measured potential value.Fix). The closer the measured potential value from the predefined end point is. the online determination of the drift during analysis has enabled a so-called "drift stop" to be used as a termination parameter.e. i.6 Termination parameters for both coulometric and volumetric KF titration The KF titration can be terminated using various parameters. pyridine-free reagents with a faster reaction rate. and improved KF titration stands (i. This parameter shortens the titration time and leads to repeatable results.e. Later on. the pulse height can be automatically changed by the system if in the titration method the control parameter “Generator current” is set to “Automatic”. The coulometer provides two different modes for iodine generation under the control parameter “Rate”: 1. the slower is the generation of iodine.METTLER TOLEDO Good Titration PracticeTM in KF Titration The iodine generation rate in the C20/C30 Coulometric Compact Karl Fischer Instruments depends on the distance from the end point. 200 and 100 mA. minimum titration time 22 .e. a delayed switch-off time of 10 to 20 seconds was set at the end point. or it can be set to a specific value (“Generator current” .e. pulse frequency and pulse height (mA) are used as variables by the instruments. Variation of pulse length (time). then the titration was stopped.25 µL for a 5 mL burette). The iodine generation starts slowly.

Typical delay time: 5 . Typical absolute drift stop value: 3 µg/min (coulometric). Typical value for the relative drift stop = 2-5 μg/min (coulometric). 10 µg/min (volumetric) • Advantage: Independent on the titrant concentration.15 seconds (Coulometric/Volumetric) • • Advantage: well-known method. 23 . 15 s) following the addition or generation of iodine. . Absolute drift stop Termination occurs as soon as the actual drift drops below the predefined absolute drift value. otherwise the termination criterion is never satisfied. otherwise the termination criterion will never be reached.e. Disadvantage: The minimum rate must be adapted to the initial drift and the titrant concentration. titrant concentration (volumetric) and side reactions. Thus.Maximum titration time The titration is terminated after the defined time. After the defined time has elapsed. Disadvantage: The value optimized to the initial drift.g.m the drift before titration) and the relative drift.METTLER TOLEDO Good Titration PracticeTM in KF Titration Delay time The titration is terminated when the potential remains below the end point for a defined time (e. the absolute drift stop value must be greater than the initial drift. The smallest increment must be sufficiently large to compensate the drift. has to be t/s • Relative drift stop The titration is terminated as soon as the actual drift drops below the sum of the initial drift (i. the titration is terminated and the result is printed. easy to understand (volumetric). 5-15 μg/min (volumetric) • Advantage: independent on the initial drift. especially if working with the KF sample oven. • Advantage: This parameter ensures a high repeatability of the results.

• Advantage: This parameter ensures a high repeatability of the results. The value of the relative drift stop influences the repeatability and the titration time: • • Drift stop (low value) → better repeatability poorer repeatability → → long titration time short titration time Drift stop (high value) → In particular.METTLER TOLEDO Good Titration PracticeTM in KF Titration . this is the simplest and most universal parameter to use. Two-component reagent: A relative drift stop value of 5 to 15 µg/min is an optimum value for achieving good repeatability. volumetric). This parameter is independent of the the initial drift (coulometric.6.e. the following values are recommended for volumetric KF titration: One-component reagent: A relative drift stop value of 5 to 15 µg/min is an optimum value for achieving good repeatability. soluble samples You should normally choose the relative drift stop as a termination parameter. possibly resulting in poorer repeatability and lower water contents. It is recommended to be used for substances that release water slowly. and the titrant concentration (volumetric). This termination parameter is also well-suited when the internal extraction is needed to determine the water content in insoluble sample: The water contained in insoluble samples is extracted during the titration. Thus. but involves a risk that the titration will be terminated a bit too early. 3. A relative drift stop of 20 to 40 µg/min shortens the titration time without affecting the repeatability. you can terminate the titration at a higher drift (relative drift stop = 40 to 70 µg/min). This is particularly critical in connection with the "slower" reagents for ketones and aldehydes.1 Using and optimizing the termination parameters for both volumetric and coulometric KF titration The following termination criteria are most commonly used for water determination by Karl Fischer titration: Relative drift stop for trouble-free. Maximum titration time for determinations with the KF drying oven When using the drying oven. the drift at the end is often greater than the initial drift. i. Use the drift/time curve to determine this value. The final traces are only extracted very slowly.Minimum titration time Titration is not to be terminated before this time in [s] is reached (exception: the maximum volume has been reached). so 24 . A relative drift stop of 20 to 30 µg/min shortens the titration time.. you can ignore these traces. The reason for this is either a very slow release of the last traces of water or a slow thermal decomposition of the sample. If the water content is relatively high. The vaporization of water is also irregular in the final stages.

Note: To obtain accurate and reliable results you should only work with the coulometer when the drift is lower than 10 µg/min. A combination of the relative drift stop and the maximum titration time has proved effective for such samples.METTLER TOLEDO Good Titration PracticeTM in KF Titration that the repeatability of the titration termination using the drift stop parameter is poor. If the drift is greater than 10 µg/min. It gives you the best accuracy and repeatability of results. Relative drift stop/maximum titration time for problematic samples Some samples lead to a high drift value at the end of the titration. This is the case with samples that only release the final traces of water very slowly or that produce side reactions. the titration is terminated at the latest after the defined maximum time. If the drift stop value is not reached. you should take measures to reduce the drift. the maximum titration time has proven to be best termination criterion in practice. Therefore. 25 . (Set the minimum titration time equal maximum titration time). The higher drift is therefore influenced to a large extent by the sample.

The desiccant absorbs the moisture and protects the titration cell against the ingress of moisture.e. 26 . When you assemble the titration stand for the first time. there will be moisture on the glass surface of the titration cell and the inserts. However. The following rules should be observed: • • Close all openings in the titration stand. it is titrated to dryness during pretitration. Condition the titration cell before use. The Karl Fischer titration Various factors must be taken into account with Karl Fischer titration to obtain correct results. Moisture can enter the sample. the greater is its influence on the results of the Karl Fischer titration. • Protect the titration cell with a desiccant (3 Å molecular sieve and silica gel). i.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. The Karl Fischer titrator should never be installed close to a ventilator of the air conditioning system! 4. The total moisture can be titrated more quickly by gently moving the vessel from side to side so that solvent swirls up the side of the vessel to pick up moisture adsorbed on the glass walls. The drift. Do not shake too vigorously to avoid solvent gets on the cover of the vessel. the higher the atmospheric humidity in the laboratory. The assumption that air-conditioned rooms have a lower atmospheric humidity is often not true: the majority of air-conditioning systems simply cool the air. This problem is particularly relevant in tropical climates or in coastal regions.3 hours.1 The influence of atmospheric humidity (drift determination) Atmospheric humidity represents the most relevant source of error in Karl Fischer titration. the relative humidity increases. since cold air cannot absorb as much moisture. where the relative humidity can achieve values of more than 80%. however.1 Titration stand The titration stand must be sealed as tightly as possible against atmospheric moisture. The air within the titration vessel also contains moisture. Silica gel can be regenerated over night at 150 °C. Briefly. The drying capacity of the desiccant is limited and it depends on the humidity and can be exhausted after 2 . This can take 1 . The air-conditioning system should therefore be equipped with a moisture condenser. the residual moisture dissolves more rapidly into the anolyte (solvent). remains high because the moisture present on the glass walls and the air in the titration cell diffuse only slowly into the anolyte (solvent).1. whereas molecular sieves require temperatures up to 300 °C. In this way. After the anolyte (coulometer) or the solvent (volumeter) has been added. until it is absolutely free of water.4 weeks (indicated by a colour change of the indicator of the silica gel). The factors include: • • • • the atmospheric humidity the working medium the pH of the sample the side reactions between the sample and the Karl Fischer reagent 4. the titrant and the titration stand.

On the other hand. For accurate results. or it can be entered by the user (“Request”): Source for Drift Online Determination Fix value Request Explanation Last measured value of standby The drift is determined and stored as raw result DRIFT A fixed value is defined into method The value can be entered immediately after starting sample titration The drift value is subsequently used in the calculation of the result in order to compensate for the moisture that entered the titration cell according to the following formula: Sample result = Total amount of water determined . the KF titrator continuously titrates the water that diffuses into the cell. traces of water will always find a way into the titration cell. it is also possible to use the value of a previously performed drift determination (“Determination”). if it is defined as the parameter “Source for drift: Online” in method function “Titration stand (KF stand)”. At the start of a sample titration. On the other hand. and its value is displayed on the screen. Therefore it must be taken into account when calculating the water content.1. it is necessary to quantify the amount of water entering the titration cell during titration.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. and is given in μg water/minute. this water amount is also titrated during analysis. Therefore. or a fixed value can be defined into the titration method (“Fix value”). the drift value should therefore be as low as possible and stable before the start of a titration! 27 . t.(drift * titration time). the last measured drift value is automatically stored. the drift indicates the quantity of water that enters the titration stand over a defined period. In the standby titration.2 The drift No titration stand is completely water tight. In this respect. This is achieved by titration of the dry solvent for a defined time (drift determination).

Normally this brown coloration disappears on filling the titration cell because the iodine excess is consumed. a flow occurs from the cathode compartment to the anode compartment.2. 28 . By ensuring that the level of the anolyte is higher than the one of the catholyte. However. In this case.5 cm into the electrolyte solution. The catholyte can be dehydrated with a few drops of a volumetric KF one component titrant.Then fill the anode compartment with approx. the level of the anolyte drops due to evaporation. the anolyte should be topped up from time to time with anhydrous methanol.5 mm higher than that of the catholyte. Higher anolyte level → low drift Lower anolyte level → drift is high . 5 mL from the bottle with a syringe and inject it into the generator electrode or empty an ampoule of catholyte into the generator electrode. . Note: In production. 2.2 Working with the coulometric KF instruments 4.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. . The catholyte always contains traces of water. This can be avoided as it follows: 1. 100 mL anolyte. • Titration cell with diaphragmless generator electrode . some anolyte solutions contain an excess of iodide and the solution has a brown colour.1 Filling the coulometric cell • Cell with generator electrode with diaphragm .Take approx. 100 mL electrolyte solution (anolyte) into the titration cell. when the drying oven is used. the levels slowly become the same. . .First transfer 5 mL catholyte to the cathode compartment. you must add some methanol or sample so that the color changes to yellow.Pour approx. If this is not the case. 2. 3 . . which leads to a higher drift. the level of the anolyte increases.Make sure that the level of the anolyte is approx.The generator electrode should dip approx. As soon as the stirrer is switched off.When a sample is injected into the anode compartment. the moisture enters the diaphragm and is slowly released into the anode compartment.The difference in level between the anolyte and catholyte is maintained as long as the stirrer is in operation. If the level of the catholyte is the same or higher.

3 Secure draining and filling of the titration cell: SOLVENT MANAGER The easiest and secure way of draining and filling the coulometric titration cell is performed with the external KF liquid handling device Solvent Manger. the level of the solvent or the anolyte exceeds the 150 mL mark. when using a generator electrode with diaphragm.2.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. With poorly soluble samples. the dissolving capacity of the anolyte (coulometric KF) is exhausted and an emulsion is formed. . After being used for two weeks. • • • • • 4.2 When do you have to replace the electrolyte? The electrolyte must be replaced in the following situations: • If the capacity of the electrolyte is exceeded. It is fully controlled by the titrator.2. e. and the risk of over titration increases. it is common use to replace both the anolyte and catholyte at the same time If after adding samples. The capacity is monitored by the coulometers (see operating instructions). The higher the level in the anode compartment. .Anolyte solutions (100 mL): after 1000 mg water. If an emulsion forms in the anode compartment. In practice. Any contact with the reagent is avoided during draining and refilling of the titration cell. This can happen if large amounts of samples of low conductivity are titrated. A level sensor in the waste bottle prevents from overflow. the worse the stirring efficiency will be. In the cathode compartment sulfides and mercaptans are formed that lead to an obnoxious smell and a higher drift. If the drift is too high.g.Catholyte solutions (5 mL): after 200 mg water. If an electrolyte is used for a long period without replacement. If the conductivity of the anolyte drops to a very low value. the drift slowly increases. The working principle of the Solvent Manager is illustrated in the following schematical illustrations: 29 . The Solvent Manager is located on top of the waste bottle and includes strong air pump (diaphragm pump) and an electromagnetic valve. below 10 μS. This can lead to wrong results.

METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 1a: Put the draining and reagent refill tube into the coulometric titration cell. Step 1b: Start the reagent replacement either from the manual function ‘Replace reagent’ or from a predefined Shortcut on the Home screen of the Touchscreen. Step 2: The Anolyte is drained into the waste bottle by applying vacuum. 30 .

In this configuration only draining of the titration cell is possible. An optional reagent exchange set consisting of tubes. The Solvent Manager is part of the standard delivery of the C20 and C30 Compact coulometric KF titrators.METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 3: The pump direction is switched by activation of the magnetic valve and subsequently fresh solvent is pumped into the titration cell by applying over pressure of dry air. Step 4: After a predefined time or by manual interaction the pressure within the solvent/anolyte bottle is relieved by switching the magnetic valce into the initial position. Depending on the type of the generator cell the following liquid handling actions can be performed: Diaphragmless generator cell: Replacement of the anolyte Generator cell with diaphragm: Replacement of the anolyte and draining of the catholyte 31 . drying tube and tube holder enables both draining and refilling.

then with anhydrous methanol and dry it as described above. The contaminants can originate from samples or are side products that have been formed in the cathode compartment by reduction. which leads to a higher drift. .Methanol flows through the diaphragm into the cathode compartment. The C30 provides a reagent monitoring routine which is called Reagent Control. • Thorough cleaning of the generator electrode If the generator electrode and the diaphragm are strongly contaminated. Place the empty generator electrode in the chromic acid or fill the generator electrode with chromic acid and let it flow through.This procedure should be repeated at least once. The procedure is identical to that described above.Fill the generator electrode with anhydrous methanol.Place the empty generator electrode in anhydrous methanol.METTLER TOLEDO Good Titration PracticeTM in KF Titration Note: The tubes for anolyte exchange are not left in the titration cell during titration. The generator electrode with diaphragm must be cleaned periodically because contamination accumulates in the diaphragm over a longer period of time. . especially if dirty samples are analyzed. since it would cause a higher drift value. If immediate use is required rinsing with anhydrous methanol shall be applied. Moisture and contaminants are rinsed out of the diaphragm. • Cleaning the titration vessel Clean the titration vessel with water or a suitable solvent. reagents can be replaced directly out of running method Choice of enforcing the user to replace it immediately or ask again later 4. Methanol flows through the diaphragm and rinses out moisture and contaminants. .2. Simple cleaning and drying of the generator electrode Method A: . Afterwards thoroughly rinse the generator electrode with water.4 Cleaning the coulometric KF titration cell The titration cell and both electrodes should be cleaned. the most effective cleaning agent is chromic acid. Afterwards dry the vessel at 100 °C in an oven or with a hot air drier. Drying is not necessary if you use it immediately. It provides the following: Monitoring three reagent parameters Usable life in days Capacity in mg water Number of samples When due.Afterwards dry the generator electrode at a maximum temperature of 50 °C in an oven or with a hot air dryer. • 32 . Method B: .

2) Connect the S7 connection of the generator cell with the indication electrode. and let an electrical current of about 400 mA flow across the platinum pins for 60 s by starting the KF titration: 1) Disconnect the S7 connection of the indication electrode. This leads to a higher potential jump. samples may be deposited on the surface of the electrode. so that there is a sharp drop in concentration. place the electrode in 0. The titrant may absorb moisture from the atmosphere reducing its concentration (the anhydrous methanol in the titrant is very hygroscopic) .if the desiccant on the titrant bottle is "used up". the one-component titrant. repeatable results.01 mg/mL per week. The Ohmic resistance of the electrode is increased. Their volume increases considerably with temperature. A reminder can be set to warn the user at the start of every titration that the usable life is about to expire in the predefined time range (days). a layer is formed on the platinum surface after the first few titrations. This also becomes noticeable through a dark coloration of the anolyte at the end point. We recommend to determine the titrant concentration daily.5 Cleaning the measuring electrode Generally. A significant change in temperature may occur: The Karl Fischer titrants consist of approximately 90% methanol or ethanol. As already described.if the titrant bottle is not tightly sealed. The titrant is not chemically stable. The layer should therefore not be removed by cleaning.g.3 Volumetric KF Titration: Titrant concentration The titrant concentration can change due to the following reasons: 1.5 mol/L sulfuric acid. • With heavily contaminated electrodes. Based on the chemical stability of the titrant.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. a weekly titer determination would be sufficient (the concentration of the one-component titrant changes by 0. In the global settings within the setup menu of 33 . The tightness of the titration stand and the proper functioning of the burette and the end point indication are also checked at the same time as the concentration is determined. the tightness of the titrant bottle and the desired level of accuracy. In countries where the temperature varies considerably during the course of the day and the lab is not air-conditioned. it is better to determine the concentration every 2 to 4 hours. 4. This test of the complete system by a titer determination is therefore an essential condition for accurate.2. The volumetric KF titrators enable monitoring of the usable life and life span of the titrant. However. e. This is sufficient in most cases. which prevents a good indication. 2. the indicating electrode does not need cleaning. • Clean the platinum pin with a paper tissue. 4.3. 3. 3) Stop the method when the cleaning is finished so that the polarization current at the indication electrode is stopped. the measuring electrode must be cleaned. In this case. while the two-component titrant is rather stable). .1 How often should the concentration be determined? How often the concentration is determined depends on the choice of titrant.

Under normal conditions.08 g/mol).using the same titration stand with the same volume of solvent. Rinse the burette 2 times into a waste bottle before you determine the concentration. Since it slowly dissolves in methanol.and at the same temperature. i. - 34 . . is the primary standard for Karl Fischer titration since it is stable and non-hygroscopic.3.5 mL with a 5 mL burette.e. This sample size yields an optimum titrant consumption of 1. Na2C4H4O6•2H2O (M = 230. thus the titrant concentration slightly but continuously decreases slightly when left to stand for a long time.2 Concentration determination with di-sodium tartrate dihydrate General Di-sodium tartrate dihydrate.08 g di-sodium tartrate dihydrate with the aid of a weighing boat. Determine the concentration under the same conditions as for sample analysis.3 to 2. Mix for 3 minutes to achieve complete dissolution before you start the titration. 4. Determine the weight by back weighing and enter it as sample size.Use the optimized METTLER TOLEDO method M301 Weigh between 0.e. i. Either the user is simply warned or the usage of the expired titrant is blocked. 26-50 % of burette volume. which prevents the execution of further titrations. you should first grind it to a fine powder before using it or use special Di-sodium tartrate dehydrate for Karl Fischer Titration Procedure . it contains 15. Note: 1. 2. Add it into the titration vessel. The plastic tubing is not absolutely water vapor-tight.04 and 0.: .66% of water. Make sure that nothing adheres to the beaker wall or to the electrode.METTLER TOLEDO Good Titration PracticeTM in KF Titration the titrator actions can be defined that will be applied if the usable life or life span is actually exceeded.

35 . This content is confirmed by the test certificate enclosed with every package. You can only perform one determination in 50 mL of 1:1 mixture (with 0.3 Concentration determination with Water Standard 10. They are thus protected against the ingress of moisture and can be stored for up to five years. A cloudy solution will falsify the results (i. The values that are obtained are approx. "HYDRANAL®-Water Standard 10. You cannot perform more than three determinations in 40 mL of methanol (with 0.e. The values obtained are approximately 10% too high. Thus. You must either change the solvent after every sample or use pure Solvent* for the determination. You cannot perform more than one determinations in 40 mL of ethanol (with 0. You must perform the determination in pure methanol! Less soluble. mixing time 1 minute. You can perform eight determinations in 40 mL of this mixture before you need to change the solvent. mixing time 5 minutes. You can perform six determinations in 30 mL of Solvent* before you need to change it.045 g di-sodium tartrate). Procedure To achieve an optimum consumption of 2 to 3 mL titrant with a concentration of 5 mg/mL. mixing time 1 minute.g. Less soluble.METTLER TOLEDO Good Titration PracticeTM in KF Titration Solubility of di-sodium tartrate dihydrate Di-sodium tartrate dihydrate must be completely dissolved (clear solution!) to obtain correct results.3. too high titer).05 g di-sodium tartrate dihydrate). Slightly soluble. You must perform the determination in pure methanol! Highly soluble.0 mg/g General Water standards consist of a mixture of organic solvents containing a specific amount of water.0" from Sigma-Aldrich® with 10 mg water in 10 g standard. 30% too high.0 to 1. The water standards are supplied in glass ampoules. e.5 g of water standard 10.05 g di-sodium tartrate).0. Highly soluble. mixing time 2 to 3 minutes. Partially soluble. you should weigh in 1. mixing time 1 minute. Partially soluble. mixing time 2 to 3 minutes. In Solvent*/chloroform mixture 1:1 or Solvent*/decanol mixture 1:1 In Solvent*/formamide mixture 1:1 In methanol In methanol/chloroform mixture 1:1 or methanol/decanol mixture 1:1 In methanol/formamide mixture 1:1 In solvent for aldehydes and ketones (one-component reagent) In ethanol *Solvent: solvent for the two-component reagent 4. always take into account the limited solubility of di-sodium tartrate dihydrate in the most commonly used solvents for Karl Fischer titrations: In Solvent* Highly soluble.

2. or with a 10.01 mg (e. To reduce the influence of the atmospheric moisture.3. – – – 36 . Determine the weight by back weighing. Open the ampoule shortly before the measurement in accordance with the enclosed instructions. Thus. The error is minimized by rinsing and conditioning the syringe beforehand. Use the METTLER TOLEDO method M300 The water standard is highly soluble in all commonly used solvents for Karl Fischer titration and can therefore be used without restrictions.0 mg water/g for a titrant concentration of 2 or 1 mg/mL. Start the titration without any mixing time.0 µL deionized water with a 10 µL syringe.01 g as the sample size. Inject 1 to 1.5 mL at a time as an aliquot.1 mg does not satisfy the requirements for a repeatable titration. Procedure – – You should weigh between 10 and 20 µL of deionized water or water according to ISO 3696 to achieve a consumption of 2 to 4 mL titrant with a concentration of 5 mg/mL.g. The content of an ampoule is sufficient for 3 to 5 determinations. Start the titration without any mixing time. The sample should be weighed either using a balance with a resolution of 0.0 mg/g water standard. Enter 0. 4. 4. with a Hamilton microliter syringe). Rinse a 10 mL syringe with approximately 1 mL of water standard. accurate results.4 Concentration determination with pure water General When using pure water to determine the concentration.METTLER TOLEDO Good Titration PracticeTM in KF Titration – – – – – – Notes 1. 3. A balance with a resolution of 0. This is due to the very small amount of sample (10 to 20 µL) that has to be injected. METTLER TOLEDO XP205 balance) or with a 10 or 20 µL precision syringe (e. Draw the whole content of the ampoule into the 10 mL syringe. a very good deal of practice and precise working is required to obtain repeatable. Plastic syringes may introduce a small amount of moisture. In an open ampoule the liquid standard is exposed to air moisture. You can use a water standard with 1. 6. 5. Inject exactly 10. Glass syringes are better. Use a new ampoule for each new concentration determination. the whole content of the ampoule is completely drawn into the syringe. the water content is increased and thus this will falsify the results.g. it is strongly recommended determining the concentration either with di-sodium tartrate dihydrate.

It is possible to determine the titrant concentration with water in all the solvents commonly used for Karl Fischer titration.3. alcohols. You can get rid of any bubbles in the syringe by expelling the water rapidly. creams. After setting the volume. You should always observe the following points when determining the concentration with a 10 µL syringe: Precondition the 10 µL syringe for approximately one hour by filling it with water. corn.5 The solvent To determine the water content in a sample. tar products. dioxane. amount 100% Samples Solvents: toluene. lay it down on the adapter and empty it completely. the sample must release water completely. All the screws in the syringe must be tightened securely. Do not warm the syringe.METTLER TOLEDO Good Titration PracticeTM in KF Titration Notes 1. salicylic acid Foods: honey. noodles. ethereal oils Petrochemical products: gasoline. fatty creams Waxes. it may draw water out of the needle!). the largest part of the solvent mixture must always be an alcohol (most preferably methanol) to ensure that the Karl Fischer reaction is strictly stoichiometric. kerosene Pharmaceutical products: ointments. Insert the syringe through the 1 mm hole of the three-hole adapter. Always add each sample in exactly the same way. to avoid touching the glass part. suppositories Sugar products: jelly. transformer oil. hydraulic oil. Hold the syringe at right angles directly in front of your eyes to read off the value. massage oil. fat Oils: edible oil. if it is absorbent. You can use mixture of solvents to achieve complete dissolution. 2. Adjust the plunger to exactly 10. caramel. jelly bears Starch products: flour. However. - 4. Always use a syringe with a long metal shaft. potato chips Chloroform Decanol Octanol Hexanol Dodecanol Toluene Formamide 70% 50% 50% 50% (30%) 37 .0 µL. beverages Cosmetics: soaps. emulsions Petrochemical products: crude oil. diesel oil. ester Organic products: urea. wipe off any drops that have adhered to the needle with two fingers (be careful if you use a paper towel. Only freely available water undergoes reaction with the Karl Fischer reagent. yogurt. Solvent Methanol Max.

In this case. The Compact Line KF titrators are able to monitor the solvent capacity: the user can define when the solvent should be replaced by specifying the usable life. formamide effectively extracts water from starch products. 4. If exhausted. 3. The extraction capacity can be improved by increasing the temperature (e. starch products will not dissolve in it. the water will no longer be completely released. or the titration will take too long and titrant will be wasted.imidazole is used for acidic samples. The solvents that are used should contain as few water as possible (< 100 ppm). Therefore. which may be completely expended if you titrate a large number of samples with high water content. 2. too low water content.6 Dissolving capacity of the solvent The dissolving or extraction capacity of the solvent is a crucial factor in Karl Fischer titration. and . the amount of water in mg which has been titrated.e. 50°C).salicylic or benzoic acid for basic samples. it is necessary to replace the solvent timely. Once again. The titrator accumulates the total water amount continuously during titrations and reports "Solvent capacity exhausted" as soon as the specified value is exceeded. Sugar is the only type of sample that dissolves in formamide. If acidic or basic samples are titrated. or the stoichiometry of the Karl Fischer reaction will change and the results will be wrong.3. the titration of subsequent samples will then be very slow. buffering agents are first added to the solvent to ensure that the titration is quick and without side reactions: . i. This will lead to incorrect results. you must replace the solvent timely. The solvent for the two-component reagent contains SO2.METTLER TOLEDO Good Titration PracticeTM in KF Titration Notes 1. On the other hand. 38 . or by indicating the maximum number of samples to be titrated. The amount of formamide at 50 °C should not exceed 30%.g.

you will no longer be able to determine its true water content. the sample should be larger the more heterogeneous the distribution of the water. 3. 5. The sample must be representative. It floats on the surface or sinks to the bottom. oils. Use bottles with a septum stopper for liquids of very low water content. which cannot be mixed as thoroughly as liquids.g. 5. Liquids of this type must be thoroughly mixed (by shaking) before a sample is taken. With liquid samples that do not dissolve water such as oils. The sample should be taken quickly to exclude.METTLER TOLEDO Good Titration PracticeTM in KF Titration 5 Sampling 5. In such cases. 39 . i.2 Storing the sample After you have taken the sample.e. "An analysis cannot be better than the actual sample!" When sampling.1 Taking the sample When taking samples for water determination. If you have to store the sample. e. the lower the amount of moisture. Heterogeneous water distribution in samples: In non-polar liquids. the solubility of water in the sample can be increased using a solubility promotion agent such as 2-propanol. In the case of non-polar solids. the water is not uniformly dispersed. such as butter. the absorption or release of moisture. 2. or at least minimize. Use sample bottles with small openings to minimize the ingress of moisture. you should take into account the following points: 1. and thus air moisture can penetrate the plastic and absorbed by the sample.the most common source of error. The sample must therefore be taken very quickly and with a syringe or a spatula that is absolutely dry. Use a bottle with an optimum volume for the amount of sample: the smaller the gas space above the sample. it must contain the same average amount of water as the material as a whole. Hygroscopic solids may exhibit higher water content on the surface than inside if they have absorbed atmospheric moisture during storage. you should determine its water content as soon as possible. water may be separated from the sample if it is left to stand for a long time. With liquid samples. keep it in a tightly sealed bottle: Glass bottles are preferable to plastic bottles because plastic is not completely gastight. This can happen when a sample cools and the water solubility is decreased. you must be extremely careful to exclude atmospheric moisture . Substances with very low water content: Substances with a very low water content are frequently extremely hygroscopic. rinse the bottles two or three times with the sample beforehand. 4. If the water content of a sample changes during sampling due to moisture being absorbed or desorbed.

A titrant consumption of 0. the accuracy increases with the amount of sample. Water content determinations below 1000 ppm are not required to be quite as accurate: a relative standard deviation srel of 1 to 5% is generally considered as acceptable for such values. sample size Amount of water [ppm] [g] [mg] 1 10 0. For coulometric analyses.0 5000 0. Repeatable results can be obtained even with 0.0 10000 = 1% 0. the amount of sample should require a titrant consumption between 30 and 70% of the nominal burette volume.1 mg water per sample. it is recommended to use the minimum sample size given in the following table: Water content Min.05 mL is thus still acceptable when using a 5 mL burette.3 Amount of sample The amount of sample used depends on • • the expected water content. because the absorption of atmospheric moisture during sampling or sample addition becomes less important. If a high level of accuracy is required. a KF titrant with a lower concentration (1 or 2 mg/mL) has to be used.0 1000 1 1.1 1. because the absorption of air moisture during sampling and sample addition becomes less important.0 For volumetric titrations.05 mg water per sample with a titrant concentration of 1 mg/mL. For optimum accuracy with determinations in the range from 1 ppm to 1% water. the optimum amount of water is in the range from 0.01 10 8 0. and the required accuracy and precision. the accuracy is improved if larger sample amounts are used.5 to 2 mg water per sample.25 100 4 0. and the following minimum sample sizes should be used: Water content Min.METTLER TOLEDO Good Titration PracticeTM in KF Titration 5.1 to 0. the optimum amount of water is approximately 10 mg per sample. 10-50 μg water can be detected if the demand for repeatability is not too high. This corresponds to 0.08 50 5 0. approx.1 to 0.4 500 2 1. This corresponds to 7.5 mg water per sample for a 5 mL burette with a titrant concentration of 5 mg/mL. As a rule of thumb.2 1. In general. Under optimum measurement conditions. sample size [ppm] [g] 10 8 50 7 100 5 200 4 500 3 1000 2 40 . For a more accurate determination of water traces (10 ppm to 1000 ppm) by volumetric KF ttiration.5 to 17.

The intersection point of this line with the "Amount of sample" scale represents the recommended amount of sample to be used.METTLER TOLEDO Good Titration PracticeTM in KF Titration Determination of the amount of sample for a water content in the range from 1000 ppm to 100% Principle: The recommended sample size can be determined as a function of the expected water content for optimum KF analysis. Logarithmic scale! 41 . Procedure: • • • Note: Start from the optimum point (10 mg for volumetric KF. 1 mg for coulometric KF) or the recommended range The optimum point is connected by a straight line to the expected water content.

an optimum sample weight range is recommended.METTLER TOLEDO Good Titration PracticeTM in KF Titration Example: Expected water content: Optimum amount of water: Optimum sample amount: 5000 ppm 10 mg/sample 2g The Compact volumetric and colometric KF titrators support the user with a sample size calculation routine. which is accessible in the online titrations screen: Dependent on the expected water content. 42 .

1 Liquid samples When adding liquid samples. alcoholic beverages methanol. creams. 50 °C and fill it into a syringe. toluene. you can use a syringe without needle since the sample can be added via the larger hole of the three-hole adapter. The syringe is heated together with the wax. 43 . Inject the sample using a 5 or 10 mL syringe with a thick needle into the titration cell. paraffin. In the case of a volumetric Karl Fischer titrator. you must take suitable precautions to prevent atmospheric moisture from being absorbed. This prevents the sample from solidifying in the syringe during the weighing.METTLER TOLEDO Good Titration PracticeTM in KF Titration 6 Sample addition 6. Low water content Low water content Hygroscopic Viscous Very viscous ointments. suppositories b c Liquefy the sample in an oven at approx. In the case of a volumetric Karl Fischer titrator. you can use a syringe without needle since the sample can be added via the larger hole of the three-hole adapter. Inject it into the cell using a wide-bore needle. edible oils hexane. benzene glycerol. aqueous emulsions. The following procedures are suitable for the different types of liquid samples: Sample characteristics High water content Low viscosity Examples perfumes. yoghurt. ski wax. Rinse a 10 mL syringe 2-3 times with the sample Inject the sample using a 1 mL or 10 mL syringe through a septum cap. Fill the 5 or 10 mL syringe with sample after removal of the piston. Possibly warm the sample slightly to lower the viscosity. silicone oil. Store the sample in a bottle with a septum stopper to avoid moisture absorption from the air. especially with samples of low water content. mineral oils massage oil Procedure Inject the sample into the titration vessel either through a septum (KF coulometer) or through the needle hole in the three-hole adapter (volumetric KF titrator) using a 1 mL syringe with needle. honey a Waxy candle wax. hydraulic oils.

– – – – – – – – – – 44 . Replace the syringe with the remaining sample on the balance and back weigh it. the drop will adhere to the septum. Withdraw the plunger and rinse the syringe with the sample by shaking it. Start the titration.METTLER TOLEDO Good Titration PracticeTM in KF Titration Taking samples from a bottle with septum stopper After several samples have been taken. Empty the syringe (into the waste bottle) and repeat the rinsing two or three times. Air flows through the molecular sieve into the bottle when you take a sample aliquot. Fill the syringe with sample and wipe the needle with a paper tissue. you must aerate the bottle with dry air (equalize the pressure). Fill a syringe without a plunger with molecular sieves. Sample addition of liquids with the back weighing technique – Fill the syringe to a quarter with sample. To avoid this. use bottles with a septum stopper and pressure equalization. Enter the sample size in the titrator or transfer it automatically. Place the syringe (upside down) in a beaker on the balance pan and tare the balance to "0". Otherwise when the syringe is removed. Start the titration method by pressing the <Start> button Inject the sample into the titration cell through the septum stopper. seal it with cotton wool and insert it into the septum bottle using a short needle. a vacuum develops in the bottle with septum stopper and it will no longer be possible to take a sample aliquot. If the sample is hygroscopic or has a low water content (< 1000 ppm). Withdraw the plunger so that the drop at the tip of the needle is sucked back into the needle.

thus. With an optimum sample size of 1 mg water/sample. cellulose powder: – Either weigh the sample in a dry box or extract it externally. e. Hard. e. this would lead to an error of 5% to 10%. If possible. – Add the sample with a weighing boat. depending on the ambient humidity. other methods have to be used for the determination of low water content by KF coulometry in solid samples: • • • External extraction External dissolution Drying oven On the other hand. For instance. The sample should be quickly weighed and added to minimize air exposure. crystalline samples: Weighing boat – Grind hard. chocolate. salicylic acid.2 Solid samples It is not possible to directly titrate solid samples using KF coulometry . 45 . the storage of samples in a refrigerator may cause water to condense. solid fat: – Grate the product and add the sample with a spatula.g. almond paste: Cut into small pieces with scissors or a knife and add the sample with a spatula. cooled analytical mill. Sample characteristic Brittle Hard/soft Pourable Procedure e. coarse-grained samples in a closed. it is necessary to warm up such samples to room temperature in a closed vessel before weighing. it should be added under the same conditions as it was transported and stored. salts. pulverize less hard samples in a mortar. fatty e.g. Finely powdered Dusty Finely powdered with very low water content Soft – Use a weighing boat with an attached flexible tubing to add the sample: it prevents the sample from adhering to the wall of the titration vessel or to the electrode.METTLER TOLEDO Good Titration PracticeTM in KF Titration 6. about 50-100 μg water enter the anode compartment. in a volumetric KF titrator solids can be directly transferred into the titration vessel.when the titration cell is opened to add the sample. jellied fruits. jelly bears.g. For this reason.g.

chocolate cream. because the water is released if it is pressurized Waxy e. Weight of solid samples with the back-weighing technique Weigh the sample in the weighing boat. Use a weighing boat with attached flexible tubing if necessary. The water content is often lower atthe surface than inside the sample. Enter the weight in the titrator or transfer it automatically. Back-weigh the empty weighing boat. inhomogeneous e. This prevents the sample from hardening inside the syringe during the weighing process Creamy Highly viscous e. fatty. honey. Do not use a syringe. 50 °C and fill them into a syringe.METTLER TOLEDO Good Titration PracticeTM in KF Titration Soft.g. - 46 . to prevent the sample from adhering to the vessel wall or to the electrode. Add the sample into the titration vessel. butter. Tare the balance to zero. margarine. ski wax. Start the titration. edible fat: – Homogenize the sample well: the water is heterogeneously distributed. The syringe is heated up together with the wax. paraffin.g. – Add the sample with a spatula.g. suppositories: – Liquefy the samples in a drying oven at approx. sugar products – The METTLER TOLEDO Visco-Spoon™ simplifies the handling with creamy samples since it can be directly mounted into the titration stand. candles.

g. chocolate.g. grain. it is necessary to crush insoluble solids in order to gain access to the trapped water. e. e. water adsorbed on surface capillary bounded water (e. brittle Viscous Hard. organic salts. The following methods are available: Sample characteristic Very hard Procedure e. hard salts: Grind in a closed. Sample preparation Water: Example: Biological samples First of all.g. suitable sample preparations and special Karl Fischer methods are necessary to release water in these samples. brittle Moderately hard. cheese: Hard.g. pharmaceuticals Water Example: Food Example: Gypsum (Ca2SO4 * 2 H2O) Thus.: • • • • entrapped water water of crystallization (salts).g. inorganic salts. fatty Soft. almond paste (“marzipan”): Cut into small pieces with scissors or a knife. coffee beans: Crush in a mixer. jellied fruits. meat.g. e.g. sausage. berries: Reduce with a homogenizer in an external solvent.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7 Release of water from the sample Karl Fischer titration is only possible if the water in the samples is freely available. e. in plants) Water Example: Sugar. This is not the case with solids if the water is bound as. crystalline products: Pulverize in a mortar. cooled analytical mill. e. e. noodles. e. e. then reduce it further with a homogenizer in an external solvent. minerals.g. solid fat: Grate the product.g. dried fruit and vegetables. Fibrous natural products Suspensions 47 . fatty Mince the product. fruit juice extracts. vegetable juices: Reduce with a homogenizer.g.

9 0. grinding the sample additionally with a built-in homogenizer (see photos below). Water is then extracted providing the mixing time defined in the titration method is sufficiently long.g.4 1.1 Internal extraction Internal extraction is suitable for insoluble solids that release water quickly when crushed: – – Add the crushed samples into the titration vessel. using either methanol or a mixture of it as the solvent.0 1.9 srel / % 0.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7.8 1.5 8. sugar.3 1. You can speed up the extraction of water from the sample by • • In many cases.0 7.8 Solvent Formamide:methanol 2:3 at 50 °C Formamide:methanol 2:3 at 50 °C Formamide:methanol 2:3 at 50 °C Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol 48 . the homogenizer eliminates the need to use auxiliary reagents such as formamide with. potato chips.1 1.1 mg/pc 3.8 4. hazelnuts.5 1. Thermostatable vessel High–speed homogenizer Examples: Sample Flour Potato chips Ground hazelnuts Chocolate Instant coffee Dried chives Dried tarragon Aspirin Sweetener tablets Optical bleaching agent Result / % 12.3 2.4 0. etc.2 1.8 1. e. heating the solution with a thermostating titration beaker.9 0.4 1.1 4.

350 ppm) and toluene (max. Briefly. methanol decanol / octanol formamide for insoluble organic solids for fatty and dairy products (butter. edible fat) for natural substances (almonds. pepper. In particular.2 External extraction External extraction is suitable for insoluble solids that release water only slowly when crushed as well as for samples with an extremely inhomogeneous water distribution. 49 .METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. the finely crushed sample is added to a solvent with very low water content and is left to stand until the water has been released from the sample. curry) for dehydrated products for sugar (total water). 600 ppm). The extraction of water can be improved • • • by shaking the solution (mechanical shaker. sugar and starch products for sugar (surface water) The organic solvents most commonly used are: • chloroform The external extraction is carried out in four steps: Step 1: Blank value determination of the extraction solvent Solvent in septum bottle Take a solvent aliquot Water content determination of solvent = blank value B - The water content of the solvent must be much less than the one of the sample. shaking bath) placing the solution in an ultrasonic bath for a certain time or reducing the sample further with a built-in homogenizer. butter milk. water is extracted from the sample by means of a defined quantity of solvent of known water content. Provide sufficient solvent for the blank value determination so that enough solvent is available for the extraction. Pay attention to the water capacity of chloroform (max.

The larger the sample.METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 2: Weigh in solvent and sample Weigh solvent in = msolv Add sample Weigh sample = mext - Cut the sample into small pieces so that it releases its water more quickly and efficiently. Add a sufficient amount of sample. For the extraction of tablets.20 is normally used. A mechanical shaker is normally used because the extraction time is often long (at least two hours or overnight). or use an ultrasonic bath with heating. A dilution factor of 10 . Step 3: Extraction - Shake. the addition of dry quartz sand has proven useful for improving and speeding up the extraction. Shaking is the method generally used for extraction. - 50 . the smaller the relative error because the total error is calculated with respect to the sample size. or use a homogenizer.

Amount of solvent (g) Amount of sample (g) extracted with the solvent Weight of the sample aliquot (g) The detailed calculations which lead to these formulas are given in the appendix. % or ppm). take an aliquot and titrate Allow to settle Take an aliquot of the extraction solution Titrate sample The following equations are used to calculate the water content of the extracted sample: ⎛ msol B ⋅ msol ⋅ ⎜C ⋅ − ⎜ mext mext ⎝ ⎞ ⎟ ⎟ ⎠ For % : R (%) = 100 100 − C For ppm : 10 6 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − R( ppm) = 6 ⎟ mext ⎠ 10 − C ⎝ mext Water content in the sample P (% or ppm). Water content of the supernatant extraction solvent (% or ppm) %: C = (VEQ*CONC-TIME*DRIFT/1000)*0. 51 . R: C: B: msol: mext: m: Note: Blank value (water content of the solvent.METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 4: Allow settling.1/m ppm: C = (VEQ*CONC-TIME*DRIFT/1000)*1000/m .

The METTLER TOLEDO methods M305 for the volumetric KF titrator and M394 for the coulometric KF titrator are available with optimized method parameters for immediate execution.6 61.6 72.4 0.4 0.9 11.8 54. The solvent blank is determined directly from the method running in standby by pressing the ‘Start blank’ button.5 Decanol:formamide:methanol 8:2:1 Decanol:formamide:methanol 8:2:1 Decanol:formamide 1:1 Decanol:formamide:methanol 8:2:1 Methanol Methanol Formamide There is a dedicated KF method type ‘External Extraction’. the weight of the sample (mext) and the weight of the aliquot of the supernatant solution containing the extracted water (sample size m) is entered into the respective sample data fields: 52 .5 9.METTLER TOLEDO Good Titration PracticeTM in KF Titration Examples for the external extraction: KF Coulometry Sample Result / ppm srel / % Extraction solvent Sucrose (surface water) 72 4.4 4.3 0.5 0.3 0.4 0.2 Chloroform Volumetric KF Titration Sample Result / % srel / % Extraction solvent Cheese Liver sausage Mustard Chicken broth Tobacco Wool Acrylic paint 27. The weight of the solvent (msol).6 0.

for instance.e.METTLER TOLEDO Good Titration PracticeTM in KF Titration The equation for the calculation of the water content of the extracted sample is predefined in the calculation method function. reaches the saturation limit for water already at 350 ppm! 53 . In particular. in order to maximize the extraction effect and ensure that the difference between the water contents before and after extraction is as large as possible. Note: 1. The amount of sample should also take account of the absorption capacity of the solvent. The amount of sample should be sufficiently large to ensure that the amount of water in the sample is significantly greater than that in the solvent prior to extraction. The water content of the solvent should be as low as possible. the formula is automatically given. “External extraction”) in the method function “Calculation”. 3. by selecting the appropriate calculation (i. Chloroform. 2.

in % or ppm. External dissolution is suitable for soluble solids with an extremely inhomogeneous water distribution. ⎛ msol + mext ⎞ ⎛ B ⋅ msol ⎞ R(%.1/m ppm: C = (VEQ*CONC-TIME*DRIFT/1000)*1000/m B: msol: mext: m: Blank value (water content in % or ppm) of the solvent.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. or with a very low water content.8 2. only the calculation method function has to be adapted to by selecting the corresponding calculation from the list of proposed results. The dedicated method type ‘External Extraction’ and the METTLER TOLEDO methods M305 for the volumetric KF titrator and M394 for the coulometric KF titrator can be used as templates. Amount of solvent (g) after determining the blank value Amount of sample (g) extracted with the solvent Weight of the sample aliquot (g) 54 . waxes and suppositories Example: Sample Result / ppm srel / % External solvent Sucrose (total water) Naphthalene Phenol Salicylic acid Contact adhesive (“Rubber cement”) 533 35 174 116 278 4.3 formamide methanol methanol methanol chloroform The method corresponds to external extraction except that the sample dissolves completely in the external solvent.2 10.3 External dissolution External dissolution is defined as the complete dissolution of a sample in a defined amount of solvent of known water content. %: C = (VEQ*CONC-TIME*DRIFT/1000)*0. The following solvents are commonly used: • • • • methanol formamide chloroform toluene for organic solids for sugar products for petroleum oils and adhesives for tar. ppm ) = C ⋅ ⎜ ⎟−⎜ ⎟ mext ⎝ ⎠ ⎝ mext ⎠ For % AND ppm: R: C: Water content in the sample P (% or ppm) Total water content (sample + solvent). or with a high water content Pure solvents can be used to dissolve the samples. the addition of methanol is not necessary.9 5.2 1.

KF coulometry is not suitable for samples with water contents of 10-100% because a very small amount of sample would have to be used. this error is reduced. the sample is previously diluted through external dissolution to be able to titrate a larger sample aliquot. Remove approx. Draw 10 . Rinse the syringe two or three times in this way.20 mL of anolyte titrated to dryness into the syringe. If 1 g of sample has a water content of 100 ppm (= 100 µg) for instance.4 Lyophilized substance in septum bottles The extremely low water content of freeze-dried substances (e. weigh it and inject it into the septum bottle. In fact. Determine the weight by back weighing. the blank value correction is too large compared to the amount of water in the sample. 4. On the other hand. 55 . and too much titrant is consumed. foodstuffs) in septum bottles means that external extraction or external dissolution as described in the previous sections are not recommended. Direct titration is not suitable.g. 6. the error as a result of opening the titration stand will be between 10 and 30 µg. If the solid has a low water content (<200 ppm). Draw an aliquot into the same syringe again. weigh it and inject it into the titration cell. You should therefore proceed as it follows: Take an aliquot of anolyte Inject it in the septum bottle Shake Take aliquot and titrate Procedure: 1. 2. Determine the weight of anolyte injected by back weighing. Thus.METTLER TOLEDO Good Titration PracticeTM in KF Titration To obtain accurate results a large sample amount is used for substances with an inhomogeneous water distribution. 10 mL of anolyte titrated to dryness from the titration cell using a 20 mL syringe with a long needle and then return it to the titration cell. 7. 5. the error obtained by direct titration if the titration stand is opened to add the sample is too large. because a large sample amount leads to a too long titration time. biological tissue. 3. 7. Shake the bottle or place it in an ultrasonic bath for 5 minutes so that the lyophilized substance dissolves or forms a suspension. Since you are able to work with larger amounts of sample when working with this technique. serum.

Alternative procedure: 1. 4.METTLER TOLEDO Good Titration PracticeTM in KF Titration If the sample is completely dissolved: use the method type “External extraction” and the calculation for the "External dissolution" If a suspension is formed: use the method type “External Extraction” and the calculation for the "External extraction" Note: In both cases. Remove approx. because the anolyte titrated to dryness has a blank value of "0". the final result must be multiplied by 4 (factor f = 4). Draw exactly 5 mL from the septum bottle into the same syringe again and inject it into the titration cell. the water amount in the septum bottle is 4 times larger. Since ¼ of the total amount was injected. 10 mL of anolyte titrated to dryness from the titration cell using a 20 mL syringe with a long needle and then return it to the titration cell. Thus. In this way. 2. With a standard method calculation and calculate the water amount in µg. 56 . Rinse the syringe two or three times in this way. 8. 3. Draw exactly 20 mL of anolyte titrated to dryness into the syringe and inject it into the septum bottle. 5. Shake the bottle or place it in an ultrasonic bath for 5 minutes so that the lyophilized substance dissolves or forms a suspension. then you can additionally calculate the result can be given in ppm. zero must be entered for the blank value (B). If you know the lyophilized sample amount in the septum bottle. 6. 7. neither the calculation for the external extraction nor for the external dissolution are needed for this procedure using the volume instead of the mass. The accuracy of a plastic syringe is enough. The water amount in µg is determined.

you must fill the gas either into special gas sample tubes or into small steel cylinders. 600 s as termination parameters.Stop the gas flow after 1 to 2 mL titrant has been consumed. . you should titrate the gas sample directly from the source.CO2 gas can not be titrated directly since iodine reacts with CO2. . Sampling/sample addition . . .Adjust the gas stream to a constant flow rate with the control valve: 50 to 200 mL/min.With sample vessels the gas amount gas can be determined by differential weighing.g. evaporated methanol lost in the gas stream must be replaced depending on titration time and number of determinations.5 Determination of water in gases To determine the water content of gases. If not.Turn the three-way valve. The water content in ppm is calculated by entering the volume and the density. to prevent the gas from flowing into the titration vessel. The water contained in the gas is then absorbed by the liquid and can be determined by means of Karl Fischer titration in a process similar to external extraction. time" and a "Delay time" of e.Calculate the volume from the time and the gas flow rate. .Purge the sample vessel and the tubings thoroughly beforehand with the gas. . . . The gas must be directed through a water-dissolving. Three-way valve Flow meter Gas Control valve The flow rate has to be constant to determine the volume necessary to calculate the water content: gas volume = gas flow rate x time.As soon as the drift is stable again. the gas must be directed through the titration vessel for a defined period of time. . start the titration and reset the three-way valve to its original position in order to direct the gas into the titration vessel. depending on the water content of the gas.Select "Max. water-free absorption liquid in which CO2 itself does not dissolve.When titrating large quantities of gas in the same solvent.If possible. .Purge the system with the gas before you start the determination.g. hydrochloric acid. 57 .Add a sufficient amount of buffer solution into the titration vessel to determine the water content of acid gases such as e.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. Determination . to ensure that the titration is terminated after the maximum time. Notes .

Air should therefore only be used for non-oxidizable. Experiments with various gas flow rates yielded the following results: Gas flow rate Recovery [mL/min]: [%]: 108 99.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. you should use a two-stage pressure regulator so that the final pressure is in the range 0. the oven temperature should not exceed 160 °C.6. The purge gases commonly used contain moisture. chapter 7. which could react with the sample at higher temperatures. for accurate results do not select a too high gas flow rate. cf. 58 . The water is transferred to the titration cell in a current of dry inert gas (purge gas).5). chapter 7.4 – 8. If you use nitrogen from a gas cylinder. the residual moisture in the purge gas should be less than at least 10 μg/L (for coulometric determination) and 20 μg/L (for volumetric KF titration) in order to obtain accurate and repeatable results.6. and the amount of water is determined. causing the water in the sample to vaporize.5 .6.0 mg/L Therefore.: o o air with 50% humidity: approx.6. 7. If you use air for organic samples.1 Principle The sample is heated in an oven.g. 7.4) A gas stream of approx. 150 mL/min is ideal for DO308 and 70 mL/min for Stromboli (automated KF drying oven. e. that release water very slowly.9 166 99. or 2. For Karl Fischer titration.1 bar (cf. cause side reactions with the Karl Fischer reagent. the purge gases must be first dried before entering the KF oven.2 Purge gas Air contains oxygen.7 500 97.6 Determination using the drying oven This method is suitable for solids and liquids that 1. 11 mg/L nitrogen gas from a cylinder: 1.1 - The recovery rate is clearly decreasing with increasing gas flow rate. Thus. inorganic samples.

In such cases you should use the maximum titration time as termination parameter (i. especially methanol. they are rapidly exhausted. To ensure that the determination is repeatable. i.e. 2. 7. the titration starts and the released water is continuously titrated. but their water absorption capacity is low. deactivate the drift stop). In the case of KF coulometers. whereas molecular sieves requires temperatures up to 300 °C. Method 2: The water is first vaporized and then titrated afterward During a defined long mix time. The relative drift stop or the maximum titration time can be used as the termination criterion. The KF titration is then started.80 µg H2O/L 40 .6.60 s). Silica gel is appreciably better in this respect.METTLER TOLEDO Good Titration PracticeTM in KF Titration Several agents are available to dry the purge gas: Method Residual moisture Residual moisture for 200 mL/min gas flow rate (drift) Sulfuric acid. Silica gel can be regenerated over night at 150 °C. Start off with the silica gel to absorb the bulk of the water and then use molecular sieves to reduce the residual moisture to a minimum. At the end of the titration. there are two types of anolyte solutions: 59 . deactivate the drift stop).50 µg H2O/L 15 – 20 µg H2O/L 50 – 60 µg H2O/L 5 – 10 µg H2O/L 10 – 15 µg H2O/min 8 – 10 µg H2O/min 3 – 4 µg H2O/min 10 – 12 µg H2O/min 1 – 2 µg H2O/min You can use the following desiccants to dry the purge gas: – – Molecular sieves are the best drying agent as far as residual moisture is concerned. P2O5 KF one-component reagent Silica gel Molecular sieves 3 Å 50 .3 Procedure There are two different methods to perform a KF titration with the drying oven: 1.e. In order to avoid the latter you may also use the minimum time as termination parameter. Method 1: The water evolved is continuously titrated After a short mix time (20 .e. the vaporization is often very irregular. The short mix time is necessary so that a delayed vaporization of water does not lead to premature termination of the titration. Silica gel and molecular sieves have the advantage that they can be regenerated. 100% Phosphorous pentoxide. The amount depends on the gas flow rate and the type of KF reagent present in the titration cell. Passing the gas stream into the titration cell causes the anolyte (in the KF coulometer) and solvent (generally methanol in KF volumetric titrator) to vaporize. in contrast to other desiccants. With some samples the drift at the end of the titration is significantly higher than the initial drift. all the water is vaporized and transferred to the titration cell. It is therefore recommended to dry the gas with a combination of silica gel and molecular sieves. you should set the maximum titration time as the termination parameter (i. This is caused by a slow release of the final traces of water or slow thermal decomposition of the sample.

there is a small loss of water. Due to the vaporization of the methanol.1 Briefly: The less methanol is vaporized.200 mL/min. time Max.g. Make sure that the level of the anolyte does not fall below that of the catholyte (higher drift!). fibers) or with samples of low water content.g.4.2 99. It has a large glass sample boat capable of holding up to 10 cm3 of sample. and the better the recovery.e. time Max. 3. As an example data from coulometric determinations are indicated here below: Method Anolyte Gas flow rate Recovery / % 1 1 2 2 Coulomat AG Coulomat AG Oven Coulomat AG Coulomat AG Oven 166 mL/min 183 mL/min 166 mL/min 106 mL/min 99. time 60 .7 99. the recovery is not 100%. Examples: Sample Result / ppm No. the faster the water is titrated. Coulomat AG or CombiCoulomat frit): Anolyte loss at 150 . The procedure for the determination of water content is described in the operating instructions. oven temperature 200 °C: approx. An air pump is available as an optional accessory. of samples srel / % T /°C Time/min Comments Polyamide Polyethylene Motor oil Cement Cooking salt Carbon black 5547 68 842 8200 360 3583 6 6 6 6 5 5 0. time Max.200 mL/min.5 . time Max. This is particularly important with low-weight samples (e.9 9.95 98. time Max.2 1. Coulomat AG Oven): Anolyte loss at 150 . The recovery therefore depends on the amount of methanol vaporized and the method used.6.5 190 280 140 300 300 200 15 10 15 20 10 15 Max. you should replace the anolyte lost through vaporization with new anhydrous methanol.4 Manual Karl Fischer drying oven The METTLER TOLEDO DO308 drying oven can be operated in a temperature range from 50 to 300 °C. as well as a gas flow meter.5 mL/hour Anolyte containing ethylene glycol. i.2 4.8 6.e.g. 7. oven temperature 200 °C: approx.9 2.METTLER TOLEDO Good Titration PracticeTM in KF Titration – Standard anolyte solutions containing methanol (e. i. 1 mL/hour – From time to time. The DO308 oven is equipped with a gas drying unit with two bottles for silica gel and molecular sieve. dedicated anolyte to be used with a KF Oven (e.

61 9. and does not drop into the cathode compartment/ titration cell. bent drying tube. If several determinations are performed in the same solvent. Set a gas flow rate of 150-200 mL/min. 2. If the drift is higher than 15 μg H2O/min. you should proceed as follows: 7. The drift should be 5-10 μg H2O/min at a gas flow of 150 mL/min. Close the stop cock and purge the "hot zone". To check the performance of the titrator/drying oven system.7%. 3. 3. 6. Open the stop cock. Always start the titration before you place the sample in the oven to ensure that the correct drift value is adopted by the method (online drift).55% or VWR/VWR/MERCK water standard KF oven 1%. replace the silica gel and molecular sieves of the gas drying unit. Coulometer KF: The internal drying tube of the generator electrode has to be replaced with an external. Some samples have surface water that is lost as soon as the oven is purged with dry gas. 5. evaporated solvent does not condense in the drying tube.METTLER TOLEDO Good Titration PracticeTM in KF Titration Comments: 1. Then. you may use the SIGMAALDRICH HYDRANAL® water standard KF oven 5.5 to 4 mL/h for an oven temperature of 200 °C and a flow rate of 200 mL/min. Experiments using methanol as the solvent gave a recovery rate of 98% for a stream of 166 mL/min. Here a short mixing time (15 to 60 s) or the minimum titration time should be defined to prevent the titration from being terminated too early. purge the "cold zone". the evaporated solvent lost in the gas stream has to be replaced. in volumetric KF titration the methanol loss is approx. and/or replace the anolyte of the KF coulometer. This leads to a too low result. In such cases. Add the sample through the tapered joint and slide the glass boat with the sample into the oven: Guide rod with magnet Slider Glass sample boat 8. start the titration so that the drift value is automatically entered. the recovery increases to 99. For instance. If the drift is constant. Some samples require some time before water starts evaporating. do not select the parameter "Auto start". The evaporation is reduced by adding ethylene glycol (higher boiling point) to a maximum solvent ratio of 20-30%. 10. This can happen when the titration is started only after complete evaporation. For the same reason. A large amount of evaporated water cannot be fully absorbed by the solvent. If the water is titrated as soon as it begins to evaporate. . 4.

1 During a sample series: 2 3 1. STROMBOLI offers one fixed place on the sample rack for an empty sample vials in order to determine the drift value.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. including the oven temperature. 62 . After the analysis. Besides 14 places for glass sample vials.6. STROMBOLI is completely controlled by the titrator: all the parameters for the determination.5 STROMBOLI automatic oven sample changer The METTLER TOLEDO STROMBOLI oven sample changer is a drying oven for automatic Karl Fischer titration with the KF Compact Volumetric V30 and Coulometric Tititrators C30 as well as with the Titration Excellence Titrators T70 and T90. The sample vials are moved upward into the oven by a lift. 2. while a glass tube pierces the aluminum foil cover. the lift is moved downward and gravity facilitates the removal of the sample vial from the oven. The oven heats the sample to the set temperature. The drying oven can be operated in the temperature range from 50 to 300°C. The blue rubber cap seals the sample vial tightly against the oven. are included in the titration method. 3. The purge gas flows through the sample vial and the water vaporized is transported via the transfer tube into the titration cell of the coulometer.

Drift determination: The drift determination is performed with an empty vial on the first position of the sample rack. fibers) or with samples of low water content. To determine the drift value accurately. the moisture in the empty sample vial has first to be removed. The drift value is defined as the moisture entered into the titration cell by the purge gas.g. This is particularly important with light samples (e. The sample vials are sealed with self-sealing aluminum foil and a rubber cup. This takes 10-20 minutes as can be seen in the following diagram: 63 .METTLER TOLEDO Good Titration PracticeTM in KF Titration Sample vials: Rubber cap Aluminum foil Sample vial The glass sample vials have a large volume (up to 25 mL).

Nevertheless. the drift value can change with time. These method templates are based on a dedicated KF method type called ‘Stromboli’. a drift determination should still be performed at least once a day in order to check whether the drift is too high (e. they can be measured at different temperatures using the same method.the analysis times for the determination of the blank value and for each sample are the same. the moisture in the air present in the vial. the method contains a so-called sample loop. The loops run through one after the other and the samples are processed sample for sample. you can check whether the drift is constant and the new drift value can be used for the next series. suboptimum conditions. Thus. at the end of a series the blank value can be measured again and compared with the value determined at the beginning. gas flow. If the maximum titration time is used as termination criterion in the method -which is what we recommend.METTLER TOLEDO Good Titration PracticeTM in KF Titration Blank value determination: The blank value is the amount of water contained in an empty sample vial (i. a blank value determination should be performed before each series of samples since the ambient conditions (humidity. as well as the anolyte in a coulometric analysis. For each series. The blank value can also vary as a function of temperature. for example. you can enter the number of samples the series includes for each loop.e. whose optimum bake-out temperatures differ. etc. If the temperatures of successive loops are different. Important: After a blank value determination. In this case. In the same way. There are dedicated METTLER TOLEDO multi-loop methods available in the V30 (M313) and in the C30 (M396). several blank value determinations can be performed one after the other in the same loop and the mean value calculated from the results. By performing a drift determination at the end of the series or between several series. i. If. moisture in the sample vial. Performing the drift and blank value determination In general. At the start of the method. The optimum blank value is in the range of 70 .) are always slightly different. This means that the stored drift value of the previous determination will be used. The blank value should be determined before each series because the humidity can change. If this is the case. > 15 μg H2O/min). 64 . the vial used no longer has the same properties as the "fresh" sample vials. To determine the blank value as accurately as possible. In this case. The first sample of the next loop is then transferred into the oven and the water determination begins.e.e.e. one with the same properties as the sample vials into which the samples have been filled in). the silica gel and molecular sieves in the bottles of the gas drying unit can be replaced. the moisture content is somewhat lower. the blank value determination also takes the actual drift into account. a blank determination can be performed between two sample loops.300 μg water. the last sample vial that was baked out remains in the oven until the temperature has stabilized at the temperature of the next loop and the drift is low and stable. It is therefore not necessary to perform a drift determination before each series. Multiple sample series at different temperatures Several series can be started on the same sample turntable – even at different temperatures. and thus the moisture adsorbed on the glass walls is not always the same. different plastic samples have to be analyzed. With rapidly changing. The new blank value is automatically used for the blank correction. and the adsorbed moisture on the glass walls of the vial) minus the amount of water due to the drift (i. drift value x time). it is important to use a new sample vial for each blank value determination (i.g.

bent drying tube. that the inert gas stream to the gas source is closed and the system is ventilated with ambient air. motor oil) or completely vaporized (e. With STROMBOLI. 6. evaporated solvent is not condensing in the drying tube. This valve shall be used especially if inert gas sources are used.g. The amount of moisture adhering to the glass surface of the sample vials strongly depends on how the vials were treated beforehand (cleaning. see also list of results). To check the titrator/drying oven system. since it provides a leak free inert gas stream during normal operation. A sudden shutdown of power immediately switches the valve in that way. you can not only determine solids but also liquid samples. 8. The delivery tube has a T-piece that causes a small leak flow. KF Coulometer C30: The internal drying tube of the generator electrode has to be replaced with an external. This is necessary so that the KF solvent or anolyte is not aspirated into the hot sample vial if Stromboli is not properly shut down while it is still hot. and therefore it does not drop into the cathode compartment. This test also serves to check the tightness of the oven and the connection tubing 65 . Allow sample vials that have been used or cleaned to stand overnight in the atmosphere for conditioning before starting measurements.METTLER TOLEDO Good Titration PracticeTM in KF Titration Comments on the operation with the STROMBOLI oven sample changer: 1. Use the same vials for a sample series as well as for the blank value determination. This has a large effect on the blank value and thus on the result. Set a gas flow of 40–60 mL/min. An optional 3/2 way valve which is automatically controlled by STROMBOLI can be used instead of the T-piece mentioned in 1. 7. drying and storage). Therefore no precious inert gas is lost and no vacuum is applied to the system which may result in a back aspiration of the anolyte into the hot oven.g. These are partially vaporized (e. Vials that have undergone different treatment can show differences in the blank value of 50-150 μg water. 4. 3. A special (longer) gas inlet glass tube is provided to bubble gas into the liquid. 5.55% or VWR/VWR/MERCK water standard KF oven 1%. toluene. 2. you can use SIGMA-ALDRICH HYDRANAL® water standard KF oven 5. In this way.

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

Examples:
Sample Result [ppm] No. of samples srel [%] T [°C]
Max.Time

[s]

Comments

Polylactic acid 0.5 g Polymer ABS-50 T 10014 3g Polymer ABS-50 F10014 2g Motor oil 1120/03 (AA) 2g

2589

3

1.1

160, air 190, N2gas 170, N2gas 165, air

--

Stir time: Max. time: rel. drift:

600 s 300 s 3 µg/min

736

5

1.1

300

Stir time: 900 s Delay time: 300 s Stir time: 900 s Delay time: 300 s Stir time: 60 s Delay time: 300 s Very slow evaporation, not faster with 180°C, above 180°C decomposition Stir time: 60 s Delay time: 300 s Very slow evaporation, above 180°C decomposition

1312

13

0.9

300

241 261

3 4

4.4 7.9

1500

Motor oil 1034/03 (AA) 1.5 g

426 438

4 3

2.7 4.5

180, air

1800

66

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

8 Measurement results
8.1 Resolution and detection limit
The following table indicates the theoretically smallest increments of current (KF coulometric) and titrant (Volumetric KF) which could be achieved by the instruments based on their technical specifications. Therefore, these are indicative values and they should be considered as such:
C20/C30 Compact Coulometric Instrument V20/V30 Compact Volumetric Titrator Resolution: 20’000 burette steps
5 mL burette: 0.25 µL c=5 mg H2O/mL: 1.25 µg H2O/step

Theoretical smallest increment

0.1 mC
Theoretical: Resolution:

(100 mA x 1 ms)
0.01 µg H2O < 0.1 µg H2O

Detection limit (limit of detection, LOD)

10 µg
Example: 10 g sample → determ. of 1 ppm Assumptions: - Current is used for iodine generation - Generated iodine is reacting 100% with water only.

50 x resolution
5 mL burette: 12.5 µL c=5 mg H2O/mL: 62.5 µg H2O Example: 5 g sample → determ. of 12.5 ppm

The theoretically smallest current increment that can be generated by the C20/C30 Compact Coulometers is 0.10712 mC which corresponds to 0.01 μg water. However, the achievable resolution of the instrument is in the order of less than 0.1 µg H2O, whereas the detection limit (also called “limit of detection”) is approx. 10 μg water per sample. Thus with a 10 g sample, 1 ppm water can be determined. For the V20/V30 Compact Volumetric instruments, the detection limit mainly depends on • • • The resolution of the burette drive, i.e. the max. number of steps which can be achieved by the stepper motor. the burette volume size; generally, a 5 mL burette is used for volumetric KF titration. The concentration of the titrant.

8.2 Measurement accuracy
The accuracy strongly depends not only on the technical specifications of the instruments, but also on the several factors that have been already mentioned in the previous chapters: 1. Sampling (including suitable storage, if necessary) 2. Sample treatment and preparation 3. Expected water content and selection of suitable instrument 4. Selection of optimum sample size 5. Condition of the KF reagents, i.e. fresh reagents, pre-titration, low drift value, … 6. Sealed titration vessel and tight tubing, 7. Condition of the indication electrode 8. Coulometry: condition of the generating cell 9. Parameter settings in the titration method etc. 67

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

To determine the closeness of agreement between the result of measurement and the true sample value, measurements can be performed either by titrating water standards or by titrating samples with known water content. The measurement accuracy depends on all the various factors described and explained in the previous sections. The crucial factors are optimum control as well as the water content and the amount of the sample.

8.3 Repeatability
The closeness of the agreement between the results of successive measurements of the same sample can be expressed quantitatively as the relative standard deviation, srel, given as %. With optimum sample amount and control, the following values can be obtained under test conditions for repeatability. The graph shows the relative standard deviation for different water contents. In general, the repeatability of a sample series becomes worse with decreasing water content. Note that for water content below 10 ppm it is not recommended to use a volumetric technique.

100% 10% 1% 1000 ppm 100 ppm 10 ppm 1 ppm

Coulometry
Not suitable for coulometry

Volumetry
srel < 0.5 %

srel < 0.5 %

srel 5 - 0.5 % srel 5 - 0.5 % srel > 5 % srel > 5 %
Not suitable for volumetry

In the following graphs, the relative standard deviation srel (%) of several series with different water content are given as a function of the sample size:

68

sample size for different water contents: KF Coulometry KF Volumetric Titration: srel (%) 6 110 ppm 5 330 ppm 4 720 ppm 3 2 1 0 0. Therefore.METTLER TOLEDO Good Titration PracticeTM in KF Titration Relative standard deviation srel vs.5 1.0 3.0 2. A good repeatability is achieved the sample size is increased particularly for low water content values. with decreasing sample size the relative standard deviation srel becomes worse.0 5. it is necessary to use the optimum sample size in order to achieve precise results.0 Sample size (g) In both cases.25 0. 69 .

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Good Titration PracticeTM in KF Titration

9 Interferences
9.1 Effects of temperature
Temperature effects on the KF titrant The Karl Fischer titrants consist of approximately 90% methanol or ethanol. Their volume increases considerably if the temperature increases, and their concentration decreases accordingly. S. Eberius [3] specifies a correction factor of 0.0012 per degree Celsius for methanolic Karl Fischer solutions. According to ISO 760, a temperature increase of 1 °C causes a drop of 0.1% in the concentration. The titrant (in particular, the two-component KF solvent) may loose sulfur dioxide if the temperature rises. This causes bubbles to form in the titrant tubing, an effect which is worse the faster the rate at which the burette is filled. These titrators allow you to define the filling rate of the burette separately for each titrant, e.g.:
Temperature / °C < 15 15 – 30 > 30

Filling rate for one-component KF volumetric titrant / % Filling rate for two-component KF volumetric titrant / %

100 80

100 60

70 40

Titration at low temperatures You can perform Karl Fischer titrations at low temperature to eliminate undesired side reactions. The water content of peroxides, for example, can be determined at -40 °C. You must use the two-component reagent to do so, because the reaction rate of the onecomponent reagent is too slow at this temperature. Titration at high temperatures Increasing the titration temperature speeds up the dissolution of the sample or the extraction of the water from it, resulting in shorter titration times. Titrations at elevated temperature have proved particularly effective for foodstuffs, e.g. sugar, flour, potato flakes, hazelnuts, custard powder. The maximum temperature depends on the boiling point of the reagent (boiling point of methanol: 64 °C, boiling point of ethanol: 78 °C).

9.2 Side reactions
Side reactions that falsify the results can occur parallel to the Karl Fischer titration. There are mainly three side reactions that can affect the result: 1. Reaction with methanol, CH3OH Aldehydes and ketones react with methanol leading to additional water Esterification with carboxylic acids leading to additional water Ketones and aldehydes react with sulphur dioxide, a base and water (i.e. water is consumed) The reaction of iodine with e.g. oxides, hydroxides, carbonates, amines, ascorbic acid, and mercaptans leads to a higher consumption of iodine giving higher water content.

2. Reaction with water, H2O

3. Reaction with iodine, I2 -

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9.2.1 Reaction with methanol
Aldehydes and ketones: Methanol, CH3OH, reacts with aldehydes (R-CHO) and ketones (R-CO-R) to form acetals (CH3-CH(OR2)2 , and (CH3)2C(OR2)2 respectively, the latter also called ketals), as well as water: Formation of acetals:

CH3CHO + 2 CH3OH
Formation of ketals:

→ →

CH3CH(OCH3)2 + H2O (CH3)2C(OCH3)2 + H2O

(CH3)2CO + 2 CH3OH
Solution: -

Use the special reagents for aldehydes and ketones with these substances (so-called K-reagents). They contain other alcohols than methanol. - Experiments have shown that the side reaction still takes place despite these reagents. Each time acetone is determined, for example, the drift is higher than before the titration: the larger the sample, the greater the drift increase. It is therefore recommend to perform the determination with a small sample amount and to replace the solvent after two or three samples. Esterification: Methanol, CH3OH, reacts under presence of strong acids (i.e. sulfuric acid) with carboxylic acids (R-COOH) to an ester (R-O-CO-CH3) and additional water:

R-COOH + CH3OH →
Solution: -

R-COO-CH3 + H2O

First neutralize the sample using a suitable base (imidazole) before KF titration.

9.2.2 Reaction with water
Another side reaction, the bisulfite addition, occurs with aldehydes and ketones in the presence of SO2. Water is consumed in the process. Bisulfite addition:

CH3CHO + H2O + SO2 + NR R1-CO-R2 + HSO3Note: SO2 + H2O = HSO3- + H+ Solution:

→ →

HC(OH)SO3HNR R1(R2)C(OH)SO3-

- Start the titration immediately after adding the sample. - Perform a fast titration by predispensing 90% of titrant consumption This causes the water to be titrated quickly, before any bisulfite addition can take place. The "Autostart" parameter allows for the automatic start of the titration as soon as the sample has been added and water is detected.

9.3 Reaction with iodine
The Karl Fischer reaction is a REDOX reaction with iodine as the oxidizing agent. Thus, iodine may also react with readily oxidizable samples. On the other hand, iodine can also be reduced by SO2 in some samples such as e.g. oxides. Both reactions cause additional iodine being consumed, giving a false higher water content.

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The following substances can react with iodine:
Ascorbic acid Boric acid, H3BO3 Disulfite, S2O5 2– Hydroxide, OH– Mercaptans, R-SH Peroxide, R-O-O-R Sulfite, SO3 Tin(II) salts
2–

Arsenite, AsO2 – Tetraborate, B4O7 2– Iron(III) salts Hydrogencarbonate, HCO3– Nitrite, NO2
– 2– 2–

Arsenate, AsO4 3– Carbonate, CO3 2– Hydrazine, N2H4, and its derivatives Copper(I) salts Oxides, e.g. CaO, MgO, MnO2 Silanols, R3-Si-OH Thiosulfate, S2O3 2–

Selenite, SeO3 Tellurite, TeO3

Solution: The Karl Fischer titration for the majority of these substances can be performed with the aid of the drying oven, or also by performing an external extraction.

9.4 Example: reevaluation of side reactions
The water content obtained is too high if side reactions previously described have occurred. This can also be the case if a drying oven is used, and the sample slowly decomposes. Nevertheless, the correct result can be reevaluated by graphical extrapolation. Example: Water determination in red polypropylene fibers.
µg water

250 °C 160 °C 120 °C

300 200
115 mg 640 ppm

100

0

5

10

15

20 min

The determination was carried out for a period of 20 minutes (max. time) with the drying oven set to 120 °C, 160 °C and 250 °C. The following results were obtained:

120 °C 1186 ppm

160°C 1442 ppm

280°C 1955 ppm

The volume-time curve clearly indicates the occurrence of a side reaction, which becomes faster with increasing the temperature. The "water content" increases with temperature. By reevaluation using the LabX® titration PC software the actual water content can be obtained by extrapolating the titration curve to time t = 0 min (green dotted lines). The content is 115 mg water; this corresponds to a water content of 640 ppm for a sample weight of 0.18 g. The extrapolated result was confirmed by an external extraction in methanol. In fact, the result obtained with this method was 610 ppm.

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if possible increase amount of sample Wrong sample preparation and sample addition .g.Measurement electrode is not plugged in .Check whether titration stand is completely tight. .Clean the platinum pins of the measurement electrode with paper tissue .The repeatability is strongly dependent on suitable sample preparation and sample addition.Use rel.Replace molecular sieves and silica gel in drying tube .Use higher oven temperature . 1 mg water per sample is present. especially at low water content (< 1000 ppm) 73 .Increase vaporization time. increase t(max) Wrong control parameters .METTLER TOLEDO Good Titration PracticeTM in KF Titration 10 Troubleshooting 10.Replace silica gel and molecular sieve in the gas drying unit The drift remains too high during standby titration Drift is too high after the titration of a sample Side reaction with the anolyte .Homogenize sample.Measurement electrode is faulty Titration stand not protected against moisture .Grease the tapered joints Moisture from cathode compartment and diaphragm .Use smaller sample Long titration time.Increase end point Oven: water vaporizes very slowly and irregularly .1 Coulometry Problem Possible causes and action to take Anolyte is not bright yellow but dark yellow to brown Drift is too high after the pretitration of a fresh anolyte .Clean titration cell and generator electrode and dry at 50 – 80 °C . drift stop as termination parameter. .Add a small amount of one-component KF titrant to the catholyte.Increase amount of sample to ensure that approx.Lengthen vaporization time (increase t max) .Check whether titration stand is completely tight.Use t(max) as termination parameter .Increase value for rel. e. Oven: . Water distribution in the sample is not homogeneous . titration never ends Very long pretitration Poor repeatability Wet anolyte .Level of anolyte should be higher than that of the catholyte .Use a different method Oven: water not completely vaporized . .Replace anolyte .Higher oven temperature . drift stop .Replace anolyte Amount of sample too small .

For samples with very low water content < 30 ppm . at 170 °C. bad repeatability With water standard 1.2 . the Coulometer must be adjusted With water Standard KF Oven 1 %.METTLER TOLEDO Good Titration PracticeTM in KF Titration Problem Possible causes and action to take Values too low The titration was terminated too soon .Replace or repaire generator electrode.Use fix generator current 100 mA .0.Lengthen vaporization time (increase t max) .Too high value: see above “too high value” .Clean titration cell and measurement electrode Poor sample preparation and addition Samples of low water content (< 1000 ppm) are always hygroscopic. If the sample preparation and addition is not done carefully.Replace or change the anolyte .Use start cautious Oven: .1 mg/g .Add sample into KF reagents. contamination with atmospheric moisture occurs.Too low value: see above “too low value” if this does not help.Use back weighing.Extend tmin (minimum titration time) Incomplete sample addition . Checking drying oven Out of limits. 10 – 15 minutes .Sample is oxidized: use nitrogen as a purge gas Checking coulometer Out of limits.0 or 0. Sample not dissolved (emulsion) . check generator electrode.Check drift and blank value . bad repeatability Platinum parts of the generator are colored black Warning: “Conductivity too low” 74 . .Replace anolyte If this doesn’t help.use a bigger sample size up to 0. if it is defective.Add chloroform or another solvent (maximum of 30%) to the anolyte to dissolve the sample Oven: .Replace anolyte . It has no influence to the result.3 g Generator electrode is contaminated The black cover cannot be removed.Use higher oven temperature . . drift stop . Anolyte has too low conductifity .Sample not thermal stable: Use lower oven temperature .Reduce the value for rel. do not splash to the walls of the cell.Use smaller sample size Values too high The titration was too fast → overtitration .

Increase amount of sample to ensure 10 mg water per sample.METTLER TOLEDO Good Titration PracticeTM in KF Titration 10.Check whether titration stand is completely tight.Use t(max) as termination parameter . Wrong control parameters .see above Oven: .Replace molecular sieves and silica gel in drying tube .The repeatability is strongly dependent on suitable sample preparation and sample addition.Grease the tapered joints Condition Titration stand . increase t(max) Long titration time. . .Shake titration vessel The drift remains too high during standby titration Titration stand not protected against moisture .Extend tmax (maximum titration time) . Low water content (<1000 ppm)! .Increase oven temperature . e.Use "Rel. e. Side reaction of the sample with the KF reagent .Use longer mixing time or different solvents which dissolves the sample or extracts the water quicker.g. Oven: water is not completely vaporized .Increase endpoint potential Oven: water vaporizes very slowly and irregularly .2 Volumetric Karl Fischer Titration Problem Possible causes and action to take Titrated solution is dark Drift too high after pretitration of fresh solvent Overtitration . titration never ends Wrong termination parameters .g. etc. 75 .Increase vaporization time. Water distribution in the sample not homogeneous . . drying oven. external extraction. drift stop" as a termination parameter. Titration stand not protected against moisture .Homogenize sample. if possible increase amount of sample.Replace silica gel and molecular sieve in the gas drying unit Drift too high after titration of a sample The sample has not completely dissolved and continuously releases water .Extend vaporization time (increase t max) .Reduce sample size Poor repeatability of the results Amount of sample too small .Increase value for relative drift stop.Check and optimize control parameters.Use higher oven temperature .Clean platinum pins of the electrode with a paper towel.Use different method.

4 g Increasing value in the concentration determination with di-sodium tartrate Checking drying oven Out of limits.Reduce the value for rel.12 g in 40 mL. . 0. drift stop .Replace solvent . Oven: .55 % at 220 °C.Sample is oxidized: use nitrogen as a purge gas The results in a series are continuously decreasing Very slow titration with twocomponent titrant Wrong or greatly fluctuating values in the concentration determination with water Dissolving capacity of the solvent is exhausted .Use back weighing. Water as standard requires practice The use of water for the concentration determination requires experience to obtain repeatable and accurate results.Check drift and blank value . No more sulfur dioxide in the solvent . The concentration determination is correct only if the di-sodium tartrate has completely dissolved.Use higher oven temperature .METTLER TOLEDO Good Titration PracticeTM in KF Titration Problem Possible causes and action to take Values too low The titration was terminated too soon . bad repeatability 76 .Change solvent or use fresh solvent after every sample.Add chloroform or other solvent to methanol.0 is a simpler and a more dependable method.Replace the solvent frequently. If the sample preparation and addition is done carefully. With water Standard KF Oven 5. 15 – 20 minutes . Sample not dissolved .Reduce dVmax and dVmax factor.Sample is not thermally stable: Use lower oven temperature . Determination of the concentration using di-sodium tartrate or Water Standard 10. Di-sodium tartrate has only limited solubility In methanol max. contamination with atmospheric moisture occurs.Change solvent.Increase sample size up to 0.Extend vaporization time (increase t max) .Use titrant with 2 or 1 mg/mL Oven: .Samples of low water content (<1000 ppm) are always hygroscopic. For samples with low water content < 400 ppm .Reduce sample size Single values too high Control parameters too fast (= slight overtitration) . which dissolves the sample. Poor sample preparation and addition .Extend tmin (minimum titration time) Incomplete sample addition .

C20 V11 C0 V2. R-Br.1 Solid samples 11.1.pyren e.C22 V16 C0 V10 C0 Nitrocompounds V3.V5 C20.V8 C20 V10.V4. C0 V2 C20 V15 Low pKa value: phenol. indole. naphthalene > C20 Tar.V4. aminophenol Aromatic/aliphatic sulfonic acids sulfides R-S-R´ disulfides R-SS-R´ thiocyanates R-SCN V0.V4 C20 Carbamates Carboxylic acid amides Mono-/polycarboxylic acids RO-CONH2 R-CONR´.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11 Karl Fischer Titration: The Method at a Glance 11.C22 V2.g. cresol. anthracene.V7 V2.V5 C20 Ethers Linear and cyclic V2. V4 V2. nitrobenzaldehyde > C12 Stearyl alcohol. V4 C20 V15 C20 V0. e. carbazole Strongly basic: aminopyridine Reaction with methanol: naphthylamine. nitrochlorobenzene Dialkylperoxide R-OO-R Alkylperoxide R-OOH Diacyl peroxide V0. C0 Sulfur compounds Phenols V0. anisidine. V5 C20 V2. V3. toluidine Oxidizable with iodine: aminophenol Method V2. V3. C24 Hydrocarbons > C12 Biphenyl.V3.V3.V3 C20 di-Nitrobenzene.V4.V5 C20. C0 Esters Carboxylic acid ester R-COOR´ Carbonic anhydride ROCOOR´ 77 . diphenylmethanol Weakly basic pKa >8: Imidazole. salicylic acid High pKa value: 2-chlorophenol. V4 C20 V2 C20 Substance Halogenated hydrocarbons Isocyanates Ketones Examples R-Cl. bitumen V4. C0 Peroxides V2.V4. stearamide Weakly acidic: benzoic acid Strongly acidic: malonic acid. o-cresol Side reaction: naphthol. V4 C20 V2. V3. nitrotoluene.: benzamide.V3.1 Organic Chemicals Substance Acetals Aldehydes Mono-/polyalcohols Amines Examples R1-CH-(OR2)2 Chlorobenzaldehyde. C0 V2. oxalic acid Oxidizable with iodine: ascorbic acid V2. R-I R-NCO Benzophenone Method V2. V4 C20 Mercaptans V0.

C40 V2 Adhesives All-purpose glue.g.1. lotion Lipstick Soaps Toothpaste V4. Insoluble: pigments. C34 V31 C33 V2. Phosphate. V32 C20. paraffins: shoepolish. indicator dyes. H3BO3 NaOH. Na2HPO4 tert. C34 V2. dispersion dyes Waxes. C34 V10 Na2HAsO3 . NaAsO2 KHCO3 . KJ. V8 Cosmetics Creams. bitumen lubricating grease. etc. C32 V15. etc.: Na3PO4 Silicon oxide. Silicon dioxide Silanols R3Si(OH) Na2SO4. multipurpose grease V2 V2. polyurethane. V5 V5 V2 V20 V2 V5 V30. NaHCO3 Na2CO3 B2O3 . disinfectants Salves. polystyrene. creams Suppositories Tablets Lyophilized preparations V2 V4. PVC. V32 C21. V31 C32 V2. V31 C20. V31 C31. C32 Pharmaceuticals Antibiotics. CaCl2 . V31 C20. KOH MgO. 78 .METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. V32 C21. e. NH4NO3 Nitrites NaNO2 11. fungicides. ski wax Tar. C34 V2. V32 C20. oxides Halogenides Examples Method V30 C30 V34 C32 V31 C32 V21. herbicides Soluble: wool dyes. MgCl2 Cu(I) salts: CuCl2 NaH2PO4 .3 Technical products – organic Substance Agrochemicals Dyes Examples Method V2 Substance Petrochemicals Examples Method V12 C0 V7 V5. CaO NaCl. V5 V12 V2 V40. NaSO3 Na2S2O5 SnCl2 Nitrates NaNO3 . C32 V31 C32 Thiosulfates Tin(II)salts Na2S2O3.1. V30 Insecticides. poly-amides. polypropylene. ZnSO4 V2. V31 C20. glue stick Rubber cement Textile auxiliaries Surfactants powder optical brightener Plastics Polymers Polyethylene. HBO3 . C32 V31 C32 Sulfates Silicon compounds Substance Phosphates Examples Method V2.2 Inorganic chemicals Substance Arsenic compounds Bicarbonates carbonates Boron compounds Hydroxides.

V23 Cacao. ice cream Dried albumen Powdered milk V2 V13 V2. hardened fat V4. sea salt Total water: plain salt. mixed spice Mustard Adherent moisture: plain salt. instant coffee. noodles. (V30) Cheese. wood Cellulose powder Wool. almond paste Instant ice tea. (V25) V22.4 Technical products .6 Food Substance Protein products Examples Method V23 Substance Grains and starchy foods Examples Method V13. V23 V30. Zwieback Yogurt.5 Technical natural products Substance Cellulose products Fibrous materials Examples Method V30. dried vegetables and fruits Hazelnuts. sea salt V23 V24.almonds instant coffee Fats Butter. jellied fruits. mayonnaise Shortening. plaster. tobacco.. corn.inorganic Substance Building materials Fertilizers Examples Method V32 (C34) V6 Substance Minerals Detergents Examples Method V32 V30. caramel. gummi bears.1.1. Zwieback. jelly Sugar: adherent moisture Chocolate Spices Pepper. meat spread. (V5) V6 C23 V32 C34 V8 V2 V6 V5 79 . coffee beans. V23 Vegetable products V22. margerine.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. potato chips Potato flakes Dough. pudding powder. jam Honey. silk 11. rye. tea. cement Adherent moisture Zeolites Laundry detergent with brightener (hydroxides. broth Biscuits. V5 V5 Sugar and sugar products V13 V13 Sugar: total water cont. V21 Mortar. noodles. curry. candy. wheat. C30 V2 V20 Paper. perborates) without brightener Total water V30 V2 11.1.

isobutane. pentane. hexylamine Reaction with methanol: aniline. methylal C1 to C7 hexane. cyclohexene. acrylic acid V15 C0 V1 C1 V1 C1 V1 C1 V1 C1 Acid amides Dimethylformamide Sulfides.2. acetic acid > C2 propionic acid. benzene. hexanol. benzaldehyde V11 C0 saturated and unsaturated V4 C1 Alcohols Propanol. chlorobenzene. crude oil.1 Organic and inorganic chemicals Substance Acetals Examples Method V1 C1 Substance Hydrocarbons Examples Method V1 C1 Acetal. diamine Easily oxidized with iodine: hydrazine. chinoline Strongly basic: alihatic amines N-butylamine. nitrotoluene. methylethylketone Ketones V10 C10 80 . dodecane > C14 heavy oil. acetophenone. C0 Ethers Esters Halogenated hydrocarbons Dimethylether. nitrochlorobenzene Acetonitrile V16 C0 Nitrocompounds V1 C1 V10 C0 Nitriles V1 C1 V0 C0 Peroxides H2O2 V15 Carboxylic acids C1 to C2 formic acid. cyclohexane. chlorotoluene Acetone. paraffin Aldehyde Acetaldehyde. disulfides sulfonic acids Mercaptans V1. hydroxylamine V1 C1 V1 C1 Mineral acids V5 C30 V15 C0 Amines H2SO4. HCl Nitrobenzene.2 Liquid samples 11. ethyl acetate Methyl chloride. benzyl alcohol Weakly basic: N-methyl aniline heterocyclic amines pyridine. HNO3. t-butyl chloride. anisole Methyl benzoate. toluidine. petroleum. ethylal. dioxane.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. C1 Sulfurcompounds V1 C1 V0. xylene C7 to C14 gasoline. toluene.

2. brake fluid. refer to chapter 11. 81 .METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. massage oil Vegetable oils Technical oils Hydraulic oil. shampoo Method V1 V1 V1 V1 V4 Tensides and detergents Aqueous emulsions Milk products: milk. sunflower oil Pharmaceuticals and cosmetics: ethereal oils. liquor Pharmaceuticals: extrakts. silicon oil Motor oils V5 C1 V30 C30 For more details on the sample preparation. tinctures Cosmetics: perfume.3. wine.2 Foods and technical products Substance Aqueous solutions Examples Foods: spiced sauce: soy sauce beverages: beer. fungicides Acrylic enamels Emulsions in solvents V1 V1 V29 V4 C1 V7 V4 C1 V4 C1 Agrochemicals (sprays): insecticides Synthetic enamels Foods: salad oil. transformer oil. condensed milk Tensides and detergents Agrochemicals (sprays): herbicides. sample input and titration methods. cream.

120 s Direct titration with added formamide Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent / formamide 1:1 Stir time: 5 . These can be also performed using the one-component reagent.1 Volumetric methods The methods have been developed using 2-component reagents.3 Titration Methods 11.120 s V2 V3 Direct titration with added 2-propanol Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / propanol 1:1 Stir time: 60 .3.10 minutes V4 V5 V6 V7 V8 V10 V11 V12 82 . In this case methanol is used as a solvent.120 s Direct titration with added chloroform Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: KF solvent / chloroform 1:1 to 1:2 Stir time: 60 .120 s Delay time: 7 seconds.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. dProcedure V1 Direct titration Titrant: Solvent: Stir time: Direct titration Titrant: Solvent: Stir time: two component reagent 5 or 2 mg H2O/mL 40 mL KF solvent 10 s two component reagent 5 or 2 mg H2O/mL 40 mL KF solvent 60 .10 minutes Direct titration methanol free Titrant: two comp. Direct titration with added toluene Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / toluene 1:1 Stir time: 60 . reagent 5 mg H2O/mL for ketone und aldehyde Solvent: 40 mL KF solvent for ketone und aldehyde Stir time: 30 – 60 s Direct titration methanol free Titrant: two comp.120 s Direct titration with added chloroform Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / chloroform 1:5 Stir time: 60 .120 s Direct titration with added 1-decanol Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / 1-decanol 1:1 Stir time: 60 . reagent 5 mg H2O/mL for ketone und aldehyde Solvent: 40 mL KF solvent for ketone und aldehyde Start immediately (autostart) Direct titration with heat (at 50°C) Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent Stir time: 5 .

220°C Titrant: two component reagent 5 or 2mg H2O/mL Solvent: 50 mL KF solvent Stir time: 10 .20 min With drying oven at 300°C Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 50 mL KF solvent Stir time: 10 .20 min Special method for lyophilized preparations Dissolve sample in septum flask with 10-20 mL titrated solvent and inject entire solution into titration cell and titrate. 50°C Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent / formamide 1:1 Stir time: 10 .15 minutes Direct titration with neutralization Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent and 20 mL buffer or 7g imidazole Stir time: 60 .150°C Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 50 mL KF solvent Stir time: 10 .120 s Direct titration with neutralization Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent and 5 g benzoic acid Stir time: 1-2 minutes External extraction with methanol at room temperature Titrant: two component reagent 5 mgH2O/mL Solvent: 30 mL KF solvent External extraction with methanol at room temperature in sonicator Remove aliquots of extraction solution over membrane filter with syringe. Titrant: two component reagent 2 mg H2O/mL Solvent: 50 mL KF solvent Side reaction: KF titration not possible V15 V16 V20 V21 V22 V23 V24 V25 V29 V30 V31 V32 V40 V0 83 .METTLER TOLEDO Good Titration PracticeTM in KF Titration V13 Direct titration with added formamide and heat.20 min With drying oven at 160 . Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with methanol at 50 °C Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with formamide Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with 1-decanol/formamide 1:1 Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with 1-decanol/formamide/methanol 8:2:1 Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with formamide Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent / formamide 1:1 With drying oven at 110 .

3.2 Coulometric methods Method C1 Procedure Direct titration Anolyte: Catholyte: 100 mL anode reagent 5 mL cathode reagent C5 Direct titration with added chloroform Anolyte: 70 mL anode reagent and 30 mL chloroform Catholyte: 5 mL cathode reagent Direct titration methanol free Anolyte: 100 mL anode reagent for ketones Catholyte: 5 mL cathode reagent for ketones External extraction with methanol or external dissolution in methanol Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction with Methanol in sonicator Remove aliquots of extraction solution over membrane filter with syringe.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Coulometric determination not possible C10 C20 C21 C22 C23 C24 C30 C31 C32 C33 C34 C40 C0 84 . Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction with 1-decanol or external dissolution in 1-decanol Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction with chloroform or external dissolution in chloroform Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction or external dissolution in chloroform (methanol free) Anolyte: 100 mL anode reagent for ketones Catholyte: 5 mL cathode reagent for ketones With drying oven at 110-130°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 140-150°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 160-190°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 200-250°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 300°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes Special method for lyophilized preparations Dissolve sample in septum flask with 10-20 mL titrated anolyte and inject entire solution into titration cell and titrate.

S3 S10. formamide).4 Sample preparation and input 11. S11 S6. noodles. or up to approx. pepper. After sample removal keep sample sealed. the moisture will be pressed out with pre-heated syringe (with needle Ø 0. Use syringe with needle Ø 1. tea. for very thick pastes drill hole in bottom of syringe. At room temp. ice cream. Pulverize with mortar. shake or sonicate. broth Hardened fat. S10 S11 S10. S8 S10 Property Soft.g. After sample removal keep sample sealed. margarine Phenols. SiO2 Salts. creams gel. bitumen Method S7. meat grinder. In external extraction solvent (methanol. active ingredients Na-tartrate S9 S12 11. Inject into titration cell. S5 S10 S8 Paraffins. Use grate to reduce size. greasy Examples Minerals.) S8 S9 S10 syringe with needle Ø 0. S10 S2. (Select stir time so that sample dissolves completely. napthalene. honey. resinous Waxes Examples Butter. rocks e.g.4. S11 S4. tobacco. meat Jellied fruits.5 mm or without needle.: CaCO3 . greasy Soft. Let solids settle and remove aliquot of remaining solution with syringe. gummi bears. jelly. coffee. S3 S2. Zwieback Dried vegetables and fruits.8 mm ) Fill in backend of syringe Procedure Grind in sealed. wool. brittle Hard natural products Fibrous natural products Tenacious products Soft products Hard. cristalline products Wheat. shoepolish Creams. Dissolve sample or extract water. Pulverize with mixer. (Pre-heat syringe with hair dryer or in drying oven. paper. Cut in small pieces with scissors or knife. 1-decanol. 1-decanol. almond paste. chocolate Method S1 S1. Break and disperse with high-speed mixer (up to 24000 cpm) in external extraction solvent (methanol. potato flakes Tar.4. formamide). No further preparation necessary.2 Solids: Sample input Method S1 S2 S3 S4 S5 S6 S7 Sample input finely ground sample with weighing boat finely ground sample with weighing boat finely ground sample with weighing boat with spatula with spatula or weighing boat with spatula or weighing boat with spatula Do not use syringe. Homogenize sample well.) Homogenize sample well. almonds. cooled analysis mill. 60° C.8 mm S11 S12 syringe without needle (Fill very thick samples in back of syringe) weighing boat 85 . Press through small holes e. silk Cheese. yogurt Salts. pastes Pulverized soluble Salves.1 Solids: Characteristics Property Very hard Hard. S2 S1. S10 S11 S4. Stir. brittle Soft. Melt sample.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11.

petroleum. Hygroscopic sample or low moisture content (< 1000 ppm) . 11. acetic acid Silicon oil.4.15 °C .The pressure loss during sample removal must be compensated with dried air. gasoline. average moisture content High moisture content Inhomogeneous (> 50%) (< 1000 ppm) 5 . synthetic enamels. detergents. .8 mm ME-71482 ME-71484 Septum NS24 ME-23950 Three-hole adapter ME-23982 86 . . Boiling point 5 .5 Accessories for sample input Syringe Injection needle Weighing boat.Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe. after-shave Beverages. Turbid liquid sample Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe.2 mm ME-71483 ME-23951 ME-51107668 10 mL 0.Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe.8 mm) Inhomogeneous emulsions . salad oil Perfume. acetone.Cool sample to approx. .Rinse syringe with sample 2-3 times (pull up and discard) and condition for 5 minutes. crude oil.8 mm) Injection with syringe Procedure Fluid liquid sample Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe. .METTLER TOLEDO Good Titration PracticeTM in KF Titration 11.8 mm) to remove fresh sample from sample flask and inject this into titration cell through septum or needle hole of three-hole adapter.8 mm) Injection with syringe (without or with needle Ø 1.8 mm). H2SO4.Keep sample in a septum flask. Samples with high moisture content (> 50%) Rinse syringe with sample 2-3 times.15°C Examples Propanol. milk. acetone. L2 L3 L4 L5 Injection with syringe L6 Injection with syringe after sample homogenization (with needle Ø 0.5 mm) Injection with syringe after cooling sample (with needle Ø 0.3 Liquids: Characteristics Property Liquid Turbid Low boiling point Hygroscopic Low moisture content Non-hygroscopic. . For each titration use 1 mL syringe (with needle Ø 0.4. glycerine Hexane.Inject sample into titration cell through septum or needle hole of three-hole adapter with 10 mL syringe (with needle Ø 0.4 Liquids: Sample input Method L1 Sample input Injection with syringe (with needle Ø 0.4. cream Method L1 L2 L3 L4 L4 L1 L5 L6 11. toluene. . glycerine Acetaldehyde Methanol. glass Visco-Spoon™ 1 mL ME-71492 1. 0°C in ice bath. aqueous emulsions Acrylic enamels.Remove sample immediately.Homogenize thoroughly by shaking or stirring prior to sample removal.

C. Part V. Potentiometric measurements”. G.W. Chim. Chem. SEUBERT A. S. 203 . 75-80 (1978). 309. Chem.. Anal.. 312. Electroanal. 395-403 (1977). Chem. Anal. Fresenius Z. “Mechanism and reaction rate of the Karl Fischer titration reaction.. Chem. 75. Chem. Einkomponenten Reagentien“. „Kinetics and stoichiometry in the Karl Fischer solution“. „Wasserbestimmung mit Karl-Fischer-Lösung“. See literature references in: EBERIUS. Anal.. E. Chem. “Mechanism and reaction rate of the Karl Fischer titration reaction. Chem 368. 1999 (in German). Thesis University of Hannover. Anal. Anal. Part III. Chem. “Untersuchungen zur Karl-Fischer-Reaktion”. „Karl-Fischer Reagentien ohne Pyridin. KOK... Acta. Verlag Chemie Weinheim (1954) / (in German).396 (1981). Fresenius J. 123-125 (1981). Both publications from: SEUBERT. Chem.. Electroanal. „Karl-Fischer Reagentien ohne Pyridin. F. Neue Eichsubstanzen“. 394 . J. 215 – 219 (1959).. W. VERHOFF. E. „The Dead-Stop End Point – As Applied to the Karl Fischer Method for Determining Moisture“.C.4. Ind. Rotating ring disk electrode meassurement .. VERHOFF. “Reaktionsmechanismen in der Karl-Fischer-Lösung“. J. 31 (2).. WÜNSCH. VERHOFF. Analytical implications”. GRÜNKE. Rotating ring disk electrode meassurement“. MEYER. 1988 (in German). Z. WÜNSCH. E. E. [9] WÜNSCH. E. “Mechanism and reaction rate of the Karl Fischer titration reaction.. SEUBERT A. Zweikomponenten Reagentien mit Imidazol“. 2407 . 705-717 (1976). 256-260 (1989) (in German). Anal. Fresenius Z.. M. SCHOLZ. BRYANT. PhD. [10] GRÜNKE.207 (1980). 86..S. SCHOLZ. BUNSEN. BOYD. 306. A. J. BARENDRECHT. 265 (1853). 94. VERHOFF.. SCHOLZ. Chem. Anal. R. SCHOLZ. [3] [4] [5] [6] [7] 87 . COFINO. 30-32 (1981).J. “Analytical Procedures Employing Karl Fischer Reagent I. [8] SCHOLZ.. Diploma-Thesis at the University of Hannover / Germany. BARENDRECHT. 407-415 (1978). HOPFKINSON. Anal. . 86. 1. Chem. Fresenius Z. C. Amer. J.. Soc. First and second order catalytic currents at a rotating disk electrode“. 394 . „Mechanism and reaction rate of the Karl Fischer titration reaction. Chem. M. Fresenius Z. “Mechanism and reaction rate of the Karl Fischer titration reaction.. J. „Karl-Fischer Reagentien ohne Pyridin. Chem. Angew. VERHOFF.396 (1935). Chem. Anal. G. “Nebenreaktionen in Karl-Fischer-Reagenzien ”. P. Part IV.C. Chem. Part I. 272 – 274 (1943). G. Anal. E. S. 71. 93. Liebigs Ann. A. Chem. J. 305-315 (1976). “Determination of Water by Titration with Coulometrically Generated Karl Fischer Reagents”. W.. J. SMITH. Auflage. MITCHELL jr. BARENDRECHT. Part II. 334. Fres.. 139-147 (2000). Ed. Anal. WERNIMONT. J.2412 (1939)..C.. Fres. „Neues Verfahren zur massanalytischen Bestimmung des Wassergehaltes von Flüssigkeiten und festen Körpern“. J. Chem. 48. W. Nature of the Reagent”. J.6 References [1] [2] FISCHER. E. J. Electroanal. Electroanal.M.comparison with the aqueous system“... „Karl-Fischer Reagentien ohne Pyridin Genauigkeit der Wasserbestimmung“. 460-464 (1982)..C. 303. 309. 15 (4). D. Th. Z. “Karl-Fischer Reagentien ohne Pyridin“. E. 16-21 (1989) (in German). E. 334. “Stöchiometrie und Kinetik der Karl-Fischer –Reaktion in Methanol als Reaktionsmedium”. Fresenius Z. Eng. 61... K. G..METTLER TOLEDO Good Titration PracticeTM in KF Titration 11.

1984.Theorie und Praxis“. Springer Verlag Berlin. SCHOLZ.METTLER TOLEDO Good Titration PracticeTM in KF Titration [11] LANZ... „Untersuchungen einer Karl-Fischer-Reaktion“. Diploma-Thesis at the University of Hannover / Germany..30918 Seelze / Germany. K. WIELAND.... G. 2006. 1985. Food Chemistry 96. E. 11.5 Additional literature HYDRANAL®-Manual. „Eugen Scholz Reagents for Karl FischerTitration“.. 431-435 (2006). DE AGOSTINI A. „Wasserbestimmung durch Karl-Fischer-Titration . M. Darmstadt / Germany. „Karl Fischer Titration“. SCHÖFFSKI. DE CARO C. "Coulometric Karl Fischer titration with a diaphragm-free cell: Cell design and applications". 1989 (German) 88 . GIT Verlag GmbH. RÜEGG K.A. Sigma-Aldrich Laborchemikalien GmbH. D.

For ppm : R (ppm ) = 10 6 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − ⎟ mext ⎠ 10 6 − C ⎝ mext since 1 = 106 ppm. WTOT : Water content of the supernatant extraction solvent (% or ppm) WL : mL : mP : Thus: 1) 2) 3) 4) 5) 6) 7) For % : C ⋅ [msol + (mext ⋅ R )] = R ⋅ mext + B ⋅ msol R C B msol mext Blank value (water content of the solvent. WP: This is what we get from the calculation in the KF method. Amount of solvent (g) after determining the blank value Amount of sample (g) extracted with the solvent C ⋅ msol + C ⋅ mext ⋅ R = R ⋅ mext + B ⋅ msol C ⋅ mext ⋅ R − R ⋅ mext = B ⋅ msol − C ⋅ msol R ⋅ (C ⋅ mext − mext ) = B ⋅ msol − C ⋅ msol R= 1 ⋅ (B ⋅ msol − C ⋅ msol ) (mext ⋅ (C − 1)) R= R= 1 ⋅ (C ⋅ msol − B ⋅ msol ) (mext ⋅ (1 − C )) since 1 1 =− 1− C C −1 1 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − ⎟ mext ⎠ 1 − C ⎝ mext R (%) = 100 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − ⎟ mext ⎠ 100 − C ⎝ mext since 1 = 100%. % or ppm).METTLER TOLEDO Good Titration PracticeTM in KF Titration 12 Appendix 12. Water amount after extraction = Water amount before extraction WTOT•(mL + (mP•WP) ) = WP•mP + WL•mL where Water content in the sample P (% or ppm). The sample P used for the extraction is not dissolved.1 Formula for the external extraction Principle: • • The water amount (in grams) after extraction is equal to the water amount before extraction. 89 .

the total volume is increased. Thus. Water amount after dissolution = Water amount before before dissolution WTOT•(mL + mP) = WP•mP + WL•mL where WP: WTOT : WL : mL : mP : Thus: 1) 2) 3) 4) C ⋅ [msol + mext ] = R ⋅ mext + B ⋅ msol Water content in the sample P (% or ppm) This is what we get from the calculation in the KF method.1% SIGMA-ALDRICH HYDRANAL®-Water Standard 0. ppm ) = C ⋅ ⎜ ⎟−⎜ ⎟ mext ⎝ ⎠ ⎝ mext ⎠ 12. The sample P used for the external dissolution is completely dissolved into the solvent. Amount of solvent (g) after determining the blank value Amount of sample (g) extracted with the solvent R C B msol mext C ⋅ msol + C ⋅ mext = R ⋅ mext + B ⋅ msol R ⋅ mext = C ⋅ msol + C ⋅ mext − B ⋅ msol ⎛ msol + mext ⎞ ⎛ B ⋅ msol ⎞ R = C ⋅⎜ ⎟−⎜ ⎟ mext ⎝ ⎠ ⎝ mext ⎠ For % and ppm: ⎛ msol + mext ⎞ ⎛ B ⋅ msol ⎞ R(%.00 mg/g (1000 ppm) b) For measurements with an oven: VWR/VWR/MERCK APURA Water standard oven 1% (tungstate) SIGMA-ALDRICH HYDRANAL®-Water Standard KF-Oven 5.3 Standards for Karl Fischer coulometry a) For direct measurements: VWR/VWR/MERCK APURA water standard 0.METTLER TOLEDO Good Titration PracticeTM in KF Titration 12.01% VWR/VWR/MERCK APURA water standard 0. in % or ppm. Total water content (sample + solvent).2 Formula for the external dissolution Principle: The water amount (in grams) determined by titration is the sum of the water amounts present in the solvent and in the sample.1 mg/g (100 ppm) SIGMA-ALDRICH HYDRANAL®-Water Standard 1.55% (potassium citrate monohydrate) The water content is declared on a test certificate supplied with every vial. Blank value (water content in% or ppm) of the solvent. 90 .

4. etc. Octanol or hexanol can be added to the anolyte to improve the solubility of these samples. 12. acetamide. In this case. part of the water content is not measured.METTLER TOLEDO Good Titration PracticeTM in KF Titration 12. For cells with diaphragm: Methanol-based reagents: anolyte: HYDRANAL® Coulomat AG (SIGMA-ALDRICH) APURA combiCoulomat frit (VWR/VWR/MERCK) catholyte: HYDRANAL® Coulomat CG (SIGMA-ALDRICH) APURA combiCoulomat frit (VWR/VWR/MERCK) Ethanol-based reagents: anolyte: HYDRANAL® Coulomat E (SIGMA-ALDRICH) catholyte: HYDRANAL® Coulomat E (SIGMA-ALDRICH) Methanol-based reagents: electrolyte:HYDRANAL® Coulomat AD (SIGMA-ALDRICH) - For cells without diaphragm: - APURA combiCoulomat fritless (VWR/VWR/MERCK) 12. the anolyte must be immediately replaced. A number of different anolytes are available to dissolve the various types of samples encountered in practice.4. nitrocompounds. edible oils. etc. alcohols. For cells with diaphragm: Methanol-based reagents: anolyte: HYDRANAL® Coulomat AG-H (SIGMA-ALDRICH) contains approx. more solvent can be added to the anolyte. chlorinated hydrocarbons (up to C10). If the sample does not completely dissolve.4 Reagents and solvents for coulometric analysis To determine its total water content. hydrocarbons (C10 to C20). 30% hexanol APURA combiCoulomat frit (VWR/VWR/MERCK) + 30% hexanol catholyte: HYDRANAL® Coulomat CG (SIGMA-ALDRICH) APURA combiCoulomat frit For cells without diaphragm: 91 . ointments. i. an emulsion is formed. This means that if an emulsion is formed in the anolyte. esters. the water content determined is lower than the actual water content of the sample.2 For samples that are poorely soluble in methanol or ethanol These include: etherial oils.e. ethers.1 For samples that are soluble in methanol or ethanol These include: hydrocarbons (up to C10). This is limited to a maximum of 30% to prevent the conductivity from falling too low. the sample must completely dissolve in the anolyte. Alternatively.

4 For ketones and aldehydes Ketones and aldehydes react with methanol to form a ketal or an acetal and water. For cells with diaphragm: Methanol-based reagents: anolyte: HYDRANAL® Coulomat A (SIGMA-ALDRICH) + 20% chloroform HYDRANAL® Coulomat AG (SIGMA-ALDRICH) + 30% chloroform APURA combiCoulomat frit (VWR/VWR/MERCK) + 30% chloroform catholyte: HYDRANAL® Coulomat CG (SIGMA-ALDRICH) APURA combiCoulomat frit (VWR/VWR/MERCK) Methanol-based reagents: electrolyte: HYDRANAL® Coulomat AD (SIGMA-ALDRICH) + 30% chloroform APURA combiCoulomat fritless (VWR/VWR/MERCK) + 30% chloroform For cells without diaphragm: - 12. Acetal formation: Ketal formation: CH3COH + 2 CH3OH → (CH3)2CO + 2 CH3OH → CH3CH(OCH3)2 + H2O (CH3)2C(OCH3)2 + H2O Special methanol-free reagents must be used for these substances. the entire titration cell must be thoroughly cleaned because even traces of methanol may cause serious interferences.METTLER TOLEDO Good Titration PracticeTM in KF Titration - Methanol-based reagents: electrolyte: HYDRANAL® Coulomat AD (SIGMA-ALDRICH) + 20% hexanol APURA CombiCoulomat fritless (VWR/VWR/MERCK) + 20% hexanol 12. etc. silicone oils. we recommend the use of a second titration cell.3 For samples that are insoluble in methanol or ethanol These include: petroleum oils. Chloroform must be added to the anolyte to ensure the solubility of these samples. For cells with diaphragm: Methanol-free reagents: anolyte: HYDRANAL® Coulomat AK (SIGMA-ALDRICH) catholyte: HYDRANAL® Coulomat CG-K (SIGMA-ALDRICH) Methanol-free reagents: electrolyte: HYDRANAL® Coulomat AK (SIGMA-ALDRICH) When changing from normal KF anolytes to ketone reagents. For cells without diaphragm: - Notes on ketones: - - 92 . transformer oils. If you measure ketones regularly.4. hydrocarbons (above C20).4. This is limited to a maximum of 30% in order to prevent the conductivity from becoming too low.

Aromatic aldehydes (e. To do this.: - For basic samples. e. acetaldehyde) are oxidized at the anode with the formation of water.g.5 to 7 (see Section 1. with reactive ketones such as cyclohexanone use only 0. The larger the sample.4. the pH value of the anolyte must be adjusted to the range 5. amines: - 93 .e.g. Coulometric KF titration cannot be used to determine these compounds. i. it is possible that the anolyte is exhausted after a few days even though no further titrations have been performed. however. 80 mL of anolyte and 20 mL HYDRANAL® buffer. Fill the anode compartment with approx. After a longer standby period. the substances can. 1 mL). easily be measured with volumetric KF determination. Choose relatively small samples (approx. Use the HYDRANAL® buffer (SIGMA-ALDRICH). It should be noted that the bisulfide-addition reaction is very strong with aromatic aldehydes. Measurement with moistened indicator paper also gives an approximate indication of the pH value of the anolyte. Fill the anode compartment with approx. the drift increases from sample to sample so strongly that the determination of the endpoint becomes difficult. etc.2 mL to 0. In these cases the pH value of the anolyte should be measured.g. e. This is why one should wait for the reverse cleavage reaction of the bisulfide compound before aborting the titration (ensure that the drift drops down again to the initial value).METTLER TOLEDO Good Titration PracticeTM in KF Titration - If you have titrated a number of ketone samples. take an aliquot of anolyte from the titration cell. Measure the pH with a glass electrode adjusted with aqueous buffers.g. 90 mL of anolyte and 5 g salicylic acid or benzoic acid.2).5 For acids and bases (pH value) A noisy titration or a sluggish end point can indicate a pH shift. Short chain aldehydes (e. formic acid. acetic acid. It is important to note that alcohols that react with ketones should not be titrated in this reagent. - For acidic samples. Basic samples must be neutralized with salicylic acid or benzoic acid. The use of imidazole increases the pH value in the anolyte. benzaldehyde) can also be determined by coulometric KF titration. the drift is higher because of the very slow side reaction. the more important the effect of side reactions becomes. The measurement should not be performed in the titration cell because the electrode introduces too much water.5 mL. With Karl Fischer titrations of acidic and basic samples. - - Notes on aldehydes: - - 12. The special reagent for ketones can also be used for other samples.

Octanol or hexanol can be added to the anolyte to improve the solubility of these samples.e. One-component reagents: Methanol-based: Titrant: HYDRANAL® Composite apura® CombiTitrant Solvent: Dry methanol Methanol-based: Titrant: HYDRANAL® Titrant apura® Titrant Solvent: HYDRANAL® Solvent Ethanol-based: Titrant: HYDRANAL® Titrant E Solvent: HYDRANAL® Solvent E (SIGMA-ALDRICH) (VWR/Merck) Two-component reagents: (SIGMA-ALDRICH) (VWR/Merck) - (SIGMA-ALDRICH) (SIGMA-ALDRICH) 12. an emulsion is formed. If it does not completely dissolve. the anolyte must be immediately replaced. Alternatively.6. the result determined is lower than the actual water content. acetamide.6.6 Titrants and solvents for volumetric analysis The sample must be completely dissolved in the anolyte to determine the total water content. ointments.1% VWR/VWR/MERCK APURA® water standard 1% SIGMA-ALDRICH HYDRANAL®-Water Standard 1.METTLER TOLEDO Good Titration PracticeTM in KF Titration 12.0 mg/g (1000 ppm) SIGMA-ALDRICH HYDRANAL®-Water Standard 10. hydrocarbons (C10 to C20). ethers. alcohols. A number of different anolytes are available to dissolve the various types of samples encountered in practice. esters.55% (potassium citrate monohydrate). chlorinated hydrocarbons (to C10).5 Water Standards for Karl Fischer volumetric titration a) For direct measurements: VWR/VWR/VWR/MERCK APURA® water standard 0. One-component reagents: 94 .0 mg/g (10’000 ppm) b) For measurements with an oven: VWR/VWR/MERCK APURA Water standard oven 1% (tungstate) SIGMA-ALDRICH HYDRANAL®-Water Standard KF-Oven 5.2 For samples poorly soluble in methanol or ethanol These include: etherial oils.1 For samples soluble in methanol or ethanol These include: hydrocarbons (to C10). The water content is declared on a test certificate supplied with every vial. more solvent can be added to the anolyte 12. part of the water content is not measured. In this case. 12. etc. edible oils. In this case. This is limited to a maximum of 50%. i. etc. nitrocompounds.

or an acetal. with the formation of water. Chloroform must be added to the anolyte to ensure the solubility of these samples. Oil apura® Solvent Oil & Fats (SIGMA-ALDRICH) (VWR/Merck) (VWR/Merck) Two-component reagents: - (SIGMA-ALDRICH) (VWR/Merck) (SIGMA-ALDRICH) (VWR/Merck) 12. etc.METTLER TOLEDO Good Titration PracticeTM in KF Titration - Methanol-based: Titrant: HYDRANAL® Composite apura® CombiTitrant Solvent: HYDRANAL® LipoSolver CM.6.4 For ketones and aldehydes Ketones and aldehydes react with methanol to form a ketal. transformer oils. Oil apura® Solvent Oil & Fats (SIGMA-ALDRICH) (VWR/Merck) (SIGMA-ALDRICH) (VWR/Merck) 12. One-component reagents: Methanol-based: Titrant: HYDRANAL® Composite apura® CombiTitrant Solvent: HYDRANAL® Solver (Crude) apura® CombiSolvent Fats Methanol-based: Titrant: HYDRANAL® Titrant apura® Titrant Solvent: HYDRANAL® Solvent CM. silicone oils.3 For samples insoluble in methanol or ethanol These include: petroleum oils. Acetal formation: Ketal formation: CH3COH + 2 CH3OH → CH3CH(OCH3)2 + H2O (CH3)2C(OCH3)2 + H2O (CH3)2CO + 2 CH3OH → Special methanol-free reagents must be used for these substances. This is limited to a maximum of 50% in order to prevent the conductivity from becoming too low. One-component reagents: 95 . MH apura® CombiSolvent Fats (SIGMA-ALDRICH) (VWR/Merck) (SIGMA-ALDRICH) (VWR/Merck) Two-component reagents: Methanol-based: Titrant: HYDRANAL® Titrant apura® Titrant Solvent: HYDRANAL® Solvent CM.6. hydrocarbons (above C20).

g. Aromatic aldehydes (e.: - For basic samples. take an aliquot of anolyte from the titration cell. The larger the sample. etc. the pH value of the anolyte must be adjusted to the range 5. With Karl Fischer titrations of acidic and basic samples. the drift increases from sample to sample so strongly that the determination of the endpoint becomes difficult. - Notes on aldehydes: - - 12. e. The measurement should not be performed in the titration cell because the electrode introduces too much water. Measurement with moistened indicator paper also gives an approximate indication of the pH value of the anolyte. The special reagent for ketones can also be used for other samples. Measure the pH with a glass electrode adjusted with aqueous buffers. e. we recommend the use of a second titration cell. Fill the anode compartment with approx. amines: 96 . i. benzaldehyde) can also be determined by coulometric KF titration.5 mL. The use of imidazole leads to a high pH value in the anolyte.METTLER TOLEDO Good Titration PracticeTM in KF Titration - Methanol-free: Titrant: Solvent: HYDRANAL® Composite 5 K apura® CombiTitrant 5 Keto (SIGMA-ALDRICH) (VWR/Merck) HYDRANAL® Medium K (SIGMA-ALDRICH) HYDRANAL® Working Medium K HYDRANAL® KetoSolver apura® CombiSolvent Keto (VWR/Merck) Notes on ketones: When changing to ketone reagents. It is important to note that alcohols that react with ketones should not be titrated in this reagent. with reactive ketones such as cyclohexanone use only 0. easily be measured with volumetric KF determination. however.g. - For acidic samples. 1 mL). If you have titrated a number of ketone samples. Choose relatively small samples (approx. Coulometric KF titration cannot be used to determine these compounds. This is why one should wait for the reverse cleavage reaction of the bisulfide compound before aborting the titration (ensure that the drift drops down again to the initial value). Short chain aldehydes (e. acetic acid.6.5 to 7 (see Section 1. the more important the effect of side reactions becomes. It should be noted that the bisulfide-addition reaction is very strong with aromatic aldehydes.g. the drift is higher because of the very slow side reaction.2 mL to 0.g.2). formic acid.e. To do this. Use the HYDRANAL® buffer (SIGMA-ALDRICH). acetaldehyde) are oxidized at the anode with the formation of water. If you measure ketones regularly.5 For acids and bases (pH value) A noisy titration or a sluggish end point can indicate a pH shift. the entire titration cell must be thoroughly cleaned because even traces of methanol can cause serious interference. the substances can. In these cases the pH value of the anolyte should be measured. 80 mL of anolyte and 20 mL HYDRANAL® buffer.

1 ppm. Ignition temp. 13 Hazards and waste disposal tips 13. 2-methoxyethanol. Irritant when inhaled. poisonous when inhaled or swallowed. Poisonous when inhaled or swallowed. Health hazard when inhaled.1 One-component reagent Composition: sulfur dioxide. The KF solvent contains: sulfur dioxide. Disposal: as an organic solvent. Health hazard when inhaled. Keep away from open flames or sparks. 2methoxyethanol or diethyleneglycolmonomethylether). sulfur dioxide.: 11 °C MAK value: 200 ppm Highly flammable. 13.4 Safety data for the KF-components and auxiliary solvents: sulfur dioxide: iodine: diethyleneglycolmonomethylether: 2-methoxyethanol: MAK-value: 200 ppm MAK-value: 0. 13. Safety: flammable to extremely flammable.2 Two-component reagent: Composition: iodine and solvent (methanol. Do not let reagent contact skin or eyes. swallowed or allowed to contact skin. and solvent (methanol. Keep container tightly closed. Do not let reagent contact skin or eyes. iodine. oxidant Ignition temp.: does not burn MAK vlaue: 200 ppm 97 methanol: o-xylene: chloroform: . buffer (imidazole). buffer (imidazole) and solvent (methanol. 13. 90 mL of anolyte and 5 g salicylic acid or benzoic acid. Health hazard when inhaled. swallowed or allowed to contact skin.: 87 °C Ignition temp. Do not let reagent contact skin or eyes. swallowed or allowed to contact skin.3 Reagents for coulometry: Composition: iodine. xylene or trichloroethaylene). tetrachloromethane.METTLER TOLEDO Good Titration PracticeTM in KF Titration - Basic samples must be neutralized with salicylic acid or benzoic acid. Skin irritant. Safety: Highly flammable. Disposal: as an organic solvent.: 28 °C MAK value: 100 ppm Flammable. Ignition temp.: 46 °C MAK value: 5 ppm Flammable. Keep container tightly closed. 2methoxyethanol or diethyleneglycolmonomethylether). Potential teratogen. Keep container tightly closed and far removed from open flames or sparks. chloroform. 2-methoxyethanol). buffer (imidazole) and solvent (methanol. Disposal: as an organic solvent. Keep away from open flames or sparks. Health hazard upon inhalation. Safety: flammable to extremely flammable. Fill the anode compartment with approx. Ignition temp. Irritant when inhaled. Irritant when inhaled.

: 6°C MAK value: 20 ppm Extremely flammable. Ignition temp.METTLER TOLEDO Good Titration PracticeTM in KF Titration 1-decanol: formamide: toluene: Health hazard when inhaled. Health hazard upon inhalation 98 . Irreversible damage possible.: 95 °C Irritant for skin and eyes. Ignition temp. Potential teratogen. Ignition temp.: inflammable MAK value: 20 ppm Irritant for skin and eyes.

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It outlines specific aspects in developing and maintaining a good routine operation with METTLER TOLEDO Compact Coulometric and Volumetric KF as well as Excellence titrators. ©09/2009 Mettler-Toledo AG Printed in Switzerland. Routine operation including PQ. development of SOPs and maintenance of the validated state of the analytical system. are two powerful tools which are meant to facilitate your daily water determination analyses and to contribute to reliable results over the whole lifetime of your instrument.com For more information Mettler-Toledo AG. evaluation.Good Titration Practice in water determination Good Titration Practice™ (GTP) in general encompasses three important steps: 1. The GTP KF brochure and the application brochure 38 containing dedicated applications on samples from various industry segments.mt. +41-44 806 77 11 Fax +41-44 806 73 50 Subject to technical changes. Analytical Sonnenbergstrasse 74 CH-8606 Schwerzenbach.e. Switzerland Tel. This brochure specifically focuses on Good Titration Practice in water determination using coulometric and volumetric Karl Fischer Titration. Evaluation of the appropriate titration system (DQ) i. specification of the analytical requirements and purchase decision 2. www. ME-51725145A Markt Support AnaChem . Installation of the selected analytical system comprising IQ and OQ and training of personnel 3. method validation.

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